Compositions comprising cyclodextrin derivatives

ABSTRACT

A stable composition for removing unwanted molecules from a surface comprises low-degree of substitution cyclodextrin derivatives. The compositions are suitable for capturing unwanted molecules from inanimate surfaces, including fabrics, including carpets, and household surfaces such as countertops, dishes, floors, garbage cans, ceilings, walls, carpet padding, air filters, and the like, and from animate surfaces, including skin, hair, and the like. The compositions can further comprise cyclodextrin-compatible and -incompatible materials, and other optional ingredients.

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This patent application claims the benefit of U.S. ProvisionalApplication Ser. No. 60/204,164 filed May 15, 2000 by R. A. Woo, et al.

TECHNICAL FIELD

[0002] The present invention relates to stable compositions can be usedfor capturing unwanted molecules in a variety of contexts, preferably tocontrol malodor including controlling malodorous molecules on inanimatesurfaces, such as fabrics, including carpets, and hard surfacesincluding countertops, dishes, floors, garbage cans, ceilings, walls,carpet padding, air filters, and the like, and animate surfaces, such asskin and hair.

BACKGROUND OF THE INVENTION

[0003] Cyclodextrin is known to form complexes with certain materials.In many compositions, cyclodextrin is used as a carrier for activematerials and thus it is desirable to form complexes betweencyclodextrin and the active materials in order for the cyclodextrin toact as a carrier for the active materials. This is especially prevalentin the pharmaceautical area, where cyclodextrins have been traditionallyused as carriers to deliver active materials. However, when cyclodextrinis used as a carrier for active material and is strongly complexed withthe active material, the cavities of the cyclodextrin molecules arefilled such that the cyclodextrin is not available to complex with othermolecules.

[0004] Surfaces, especially household surfaces such as fabrics,countertops, and the like, often contain unwanted molecules, such asmalodorous molecules. Cyclodextrin molecules are capable of capturingunwanted molecules from surfaces; however, cyclodextrin compositionsused to treat surfaces containing unwanted molecules must havecyclodextrin that is available to complex with the unwanted molecules inorder to capture and remove the unwanted molecules from the surfacebeing treated. Compositions have been disclosed that are useful forcontrolling malodor on surfaces, wherein the compositions compriseuncomplexed cyclodextrin. For example, U.S. Pat. No. 5,942,217 issuedAug. 24, 1999 to Woo et al. teach compositions for controlling malodoron surfaces wherein the compositions can comprise uncomplexedcyclodextrin and materials that are cyclodextrin-compatible, such ascyclodextrin-compatible surfactants and cyclodextrin-compatibleantimicrobial actives. The materials in these compositions are selectedsuch that they do not complex with cyclodextrin in solution, thusproviding available, uncomplexed cyclodextrin in solution to capture themalodor from the treated surfaces. The cyclodextrins suitable for use inthe compositions disclosed in the '217 patent include derivatizedcylcodextrins such as hydroxyalkyl cyclodextrins and methylatedcyclodextrins. Woo et al. teach that preferred hydoxyalkyl cyclodextrinshave a degree of substitution of from about 1 to about 14, and morepreferably from about 1.5 to about 7, wherein the total number of ORgroups per cyclodextrin is defined as the degree of substitution. Woo etal. further teach that preferred methylated cyclodextrins have a degreeof substitution of from about 1 to about 18, and more preferably fromabout 3 to about 16.

[0005] It has thus been desired to develop optimized cyclodextrincompositions that exihibit improved performance in capturing unwantedmolecules, especially malodorous molecules, by selecting appropriatecyclodextrins for use in the compositions.

SUMMARY OF THE INVENTION

[0006] The present invention relates to compositions for capturingunwanted molecules from inanimate surfaces, including fabrics, includingcarpets, and hard surfaces including countertops, dishes, floors,garbage cans, ceilings, walls, carpet padding, air filters, and thelike, and animate surfaces, such as skin, hair, and the like. Thepresent invention further relates to compositions for use in acabinet-type or bag-type apparatus for conditioning garments. Thecompositions herein for capturing unwanted molecules comprise low-degreeof substitution cyclodextrin derivatives. The use of low-degree ofsubstitution cyclodextrin derivatives in the present compositionsprovides improved performance in terms of capturing unwanted moleculesfrom treated surfaces, as compared to similar compositions comprisinghigher degree of substitution cyclodextrin derivatives. The low-degreeof substitution cyclodextrin derivatives in the present compositions arepreferably functionally-available in the compositions in order tocapture unwanted molecules from the surfaces. The present compositionscan further comprise cyclodextrin-compatible and incompatible materials,and other optional ingredients.

[0007] The low-degree of substitution cyclodextrin derivatives usefulherein are preferably selected from low-degree of substitutionhydroxyalkyl cyclodextrin, low-degree of substitution alkylatedcyclodextrin, and mixtures thereof. Preferred low-degree of substitutionhydroxyalkyl beta-cyclodextrins have an average degree of substitutionof less than about 5.0, more preferably less than about 4.5, and stillmore preferably less than about 4.0. Preferred low-degree ofsubstitution alkylated cyclodextrins have an average degree ofsubstitution of less than about 6.0, more preferably less than about5.5, and still more preferably less than about 5.0.

[0008] The present invention further relates to processes ofmanufacturing a composition suitable for capturing unwanted moleculeswherein the composition comprises low-degree of substitutioncyclodextrin derivative, cyclodextrin-incompatible material, andcyclodextrin-compatible material. The present invention also relates tomethods of using the compositions of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0009] I. Compositions

[0010] The present invention encompasses stable compositions comprisinglow-degree of substitution cyclodextrin derivative, wherein thecyclodextrin is preferably functionally-available cyclodextrin. Thecompositions can further comprise optional cyclodextrin-compatible andincompatible materials, and other optional components.

[0011] The present compositions can be either emulsions/dispersions orclear, single-phase solutions. Compositions of the present invention forcontrolling malodor on fabrics are preferably clear, single-phasesolutions and generally have a particle size of molecular aggregates,such as micelles and/or vesicles, of no greater than about 0.2 μm,preferably no greater than about 0.1 μm, and more preferably no greaterthan about 0.05 μm. Preferably, the cyclodextrin compositions of thepresent invention are clear. The term “clear” as defined herein meanstransparent or translucent, preferably transparent, as in “water clear,”and have a percent transmittance of at least about 70%, preferably atleast about 75%, and more preferably at least about 80% at 420 nm.

[0012] Compositions of the present invention such as detergentcompositions, fabric softening compositions, shampoo compositions, hardsurface cleaning compositions, and the like, are preferablyemulsions/dispersions and generally have a particle size of molecularaggregates, such as micelles and/or vesicles, of greater than about 0.05μm, preferably greater than about 0.1 μm, and more preferably greaterthan about 0.2 μm. These compositions can be clear, translucent, oropaque, dependent on the types and concentrations of materials in thecompositions.

[0013] A. Low-Degree of Substitution Cyclodextrin Derivatives

[0014] The present compositions comprise low-degree of substitutioncyclodextrin derivatives, wherein the cyclodextrin is preferablyfunctionally-available cyclodextrin. The low-degree of substitutioncyclodextrin derivatives in the present compositions are capable ofexhibiting improved complexation with unwanted molecules that arepresent on the surfaces being treated with the present compositions.When the surfaces are treated with the present compositions, thelow-degree of substitution cyclodextrin derivatives complex with theunwanted molecules, thereby more effectively removing and/or reducingthe presence of the unwanted molecules on the treated surfaces, ascompared to cyclodextrin derivatives having higher average degrees ofsubstitution, even when the low-degree of cyclodextrin derivatives areused at lower levels in the compositions.

[0015] As used herein, the term “cyclodextrin” includes any of the knowncyclodextrins such as unsubstituted cyclodextrins containing from six totwelve glucose units, especially, alpha-cyclodextrin, beta-cyclodextrin,gamma-cyclodextrin, or mixtures thereof. The alpha-cyclodextrin consistsof six glucose units, the beta-cyclodextrin consists of seven glucoseunits, and the gamma-cyclodextrin consists of eight glucose unitsarranged in donut-shaped rings. The specific coupling and conformationof the glucose units give the cyclodextrins a rigid, conical molecularstructure with hollow interiors of specific volumes. The “lining” ofeach internal cavity is formed by hydrogen atoms and glycosidic bridgingoxygen atoms; therefore, this surface is fairly hydrophobic. The uniqueshape and physical-chemical properties of the cavity enable thecyclodextrin molecules, and derivatives thereof, to absorb (forminclusion complexes with) organic molecules or parts of organicmolecules which can fit into the cavity. Many unwanted moleculesexisting on surfaces can fit into the cavity, including many malodorousmolecules. Therefore, cyclodextrins and their derivatives, andespecially mixtures of cyclodextrins with different size cavities, canbe used to complex with unwanted molecules, especially to controlmalodors caused by a broad spectrum of organic odoriferous materials,which can contain reactive functional groups. The complexation betweencyclodextrin and unwanted molecules, especially malodorous molecules,occurs particularly rapidly in the presence of water. However, theextent of the complex formation can also depend on the polarity of theabsorbed molecules (i.e. unwanted molecules). In an aqueous solution,strongly hydrophilic unwanted molecules (e.g. those which are highlywater-soluble) tend to be only partially absorbed, if at all. Therefore,cyclodextrin does not complex effectively with some very low molecularweight organic amines and acids when they are present at low levels onwet fabrics. As the water is being removed however, e.g., the fabric isbeing dried off, some of the unwanted molecules, e.g. low molecularweight organic amines and acids, have more affinity and will complexwith the cyclodextrins more readily.

[0016] Derivatives of cyclodextrins consist mainly of molecules whereinsome of the OH groups are converted to OR groups. Cyclodextrinderivatives include, e.g., those with short chain alkyl groups such asmethylated cyclodextrins, and ethylated cyclodextrins, wherein R is amethyl or an ethyl group; those with hydroxyalkyl substituted groups,such as hydroxypropyl cyclodextrins and/or hydroxyethyl cyclodextrins,wherein R is a —CH₂—CH(OH)—CH₃ or a —CH₂CH₂—OH group; branchedcyclodextrins such as maltose-bonded cyclodextrins; cationiccyclodextrins such as those containing 2-hydroxy-3-(dimethylamino)propylether, wherein R is CH₂—CH(OH)—CH₂—N(CH₃)₂ which is cationic at low pH;quaternary ammonium, e.g., 2-hydroxy-3-(trimethylammonio)propyl etherchloride groups, wherein R is CH₂—CH(OH)—CH₂—N⁺(CH₃)₃Cl—; anioniccyclodextrins such as carboxymethyl cyclodextrins, cyclodextrinsulfates, and cyclodextrin succinylates; amphoteric cyclodextrins suchas carboxymethyl/quaternary ammonium cyclodextrins; cyclodextrinswherein at least one glucopyranose unit has a 3-6-anhydro-cyclomaltostructure, e.g., the mono-3-6-anhydrocyclodextrins, as disclosed in“Optimal Performances with Minimal Chemical Modification ofCyclodextrins”, F. Diedaini-Pilard and B. Perly, The 7th InternationalCyclodextrin Symposium Abstracts, Apr. 1994, p. 49, said referencesbeing incorporated herein by reference; and mixtures thereof. Othercyclodextrin derivatives are disclosed in U.S. Pat. No. 3,426,011,Parmerter et al., issued Feb. 4, 1969; U.S. Pat. Nos. 3,453,257;3,453,258; 3,453,259; and 3,453,260, all in the names of Parmerter etal., and all issued Jul. 1, 1969; U.S. Pat. No. 3,459,731, Gramera etal., issued Aug. 5, 1969; U.S. Pat. No. 3,553,191, Parmerter et al.,issued Jan. 5, 1971; U.S. Pat. No. 3,565,887, Parmerter et al., issuedFeb. 23, 1971; U.S. Pat. No. 4,535,152, Szejtli et al., issued Aug. 13,1985; U.S. Pat. No. 4,616,008, Hirai et al., issued Oct. 7, 1986; U.S.Pat. No. 4,678,598, Ogino et al., issued Jul. 7, 1987; U.S. Pat. No.4,638,058, Brandt et al., issued Jan. 20, 1987; and U.S. Pat. No.4,746,734, Tsuchiyama et al., issued May 24, 1988; all of said patentsbeing incorporated herein by reference. Further cyclodextrin derivativessuitable herein include those disclosed in V. T. D'Souza and K. B.Lipkowitz, CHEMICAL REVIEWS: CYLCODEXTRINS, Vol. 98, No. 5 (AmericanChemical Society, July/August 1998), which is incorporated herein byreference. Examples of preferred water-soluble cyclodextrin derivativessuitable for use herein include hydroxypropyl alpha-cyclodextrin,methylated alpha-cyclodextrin, methylated beta-cyclodextrin,hydroxyethyl beta-cyclodextrin, hydroxypropyl beta-cyclodextrin,hydroxypropyl gamma-cyclodextrin, and methylated gamma-cyclodextrin.

[0017] As used herein, the term “degree of substitution,” as it relatesto cyclodextrin derivatives, refers to the total number of OR groups percyclodextrin molecule. It is understood that commercially availablecyclodextrin derivatives actually contain individual cyclodextrinmolecules having varying degrees of substitution. For example,hydroxypropyl beta-cyclodextrin having an average degree of substitutionof 3 still contains an amount of non-derivatized beta-cyclodextrin ofabout 5%, while hydroxypropyl beta-cyclodextrin having an average degreeof substitution of about 5 has an amount of non-derivatizedbeta-cyclodextrin of less than about 1%. The term “average degree ofsubstitution” thus relates to the average statistical distribution ofindividual substituted cyclodextrin molecules of a given cyclodextrinderivative. As used herein, the term “low-degree of substitution” refersto cyclodextrin derivatives in which less than about one-fourth (¼) ofthe OH groups of the cyclodextrin molecule have been converted to ORgroups.

[0018] It has been surprisingly discovered that low-degree ofsubstitution cyclodextrin derivatives provide significantly improvedperformance, as compared to similar cyclodextrin derivatives havinghigher degrees of substitution, in regard to capturing unwantedmolecules. The improved capturing of unwanted molecules, such asmalodorous molecules, by compositions comprising low-degree ofsubstitution cyclodextrin derivatives is shown hereinafter in Example 1.

[0019] The average degree of substitution of the low-degree ofsubstitution cyclodextrin derivatives useful herein generally dependsupon the particular cyclodextrin derivative. For example, hydroxyalkylbeta-cyclodextrins useful herein typically have an average degree ofsubstitution of less than about 5.0, preferably less than about 4.5, andmore preferably less than about 4.0. Alkylated cyclodextrins usefulherein typically have an average degree of substitution of less thanabout 6.0, preferably less than about 5.5, and more preferably less thanabout 5.0. A highly preferred low-degree of substitution hydroxyalkylcyclodextrin useful herein is hydroxypropyl beta-cyclodextrin having anaverage degree of substitution of about 3.3. A highly preferredlow-degree of substitution alkylated cyclodextrin is methylatedbeta-cyclodextrin having an average degree of substitution of about 4.2.The preferred cyclodextrins are available, e.g., from Cerestar USA, Inc.and Wacker USA, Inc.

[0020] The compositions herein can comprise a mixture of cyclodextrinsand derivatives thereof such that the mixture effectively has an averagedegree of substitution equivalent to the low-degree of substitutioncyclodextrin derivatives described hereinbefore. Such cyclodextrinmixtures preferably comprise high-degree of substitution cyclodextrinderivatives (having a higher average degree of substitution than thelow-degree substitution cyclodextrin derivatives described herein) andnon-derivatized cyclodextrin, such that the cyclodextrin mixtureeffectively has an average degree of substitution equivalent to thelow-degree of substitution cyclodextrin derivative. For example, acomposition comprising a cyclodextrin mixture containing 0.1%non-derivatized beta-cyclodextrin and 0.4% hydroxypropylbeta-cyclodextrin having an average degree of substitution of about 5.5,exhibits an ability to capture unwanted molecules similar to that of asimilar composition comprising low-degree of substitution hydroxypropylbeta-cyclodextrin having an average degree of substitution of about 3.3.Such cyclodextrin mixtures can typically absorb odors more broadly bycomplexing with a wider range of unwanted molecules, especiallymalodorous molecules, having a wider range of molecular sizes.Preferably at least a portion of a cyclodextrin mixture isalpha-cyclodextrin and its derivatives thereof, gamma-cyclodextrin andits derivatives thereof, and/or beta-cyclodextrin and its derivativesthereof; more preferably a mixture of alpha-cyclodextrin, or analpha-cyclodextrin derivative, and derivatized beta-cyclodextrin, evenmore preferably a mixture of derivatised alpha-cyclodextrin andderivatized beta-cyclodextrin; and most preferably a mixture ofhydroxypropyl alpha-cyclodextrin and hydroxypropyl beta-cyclodextrin,and/or a mixture of methylated alpha-cyclodextrin and methylatedbeta-cyclodextrin.

[0021] The cyclodextrins and derivatives used herein are preferablyincorporated in the present compositions such that they arefunctionally-available. As used herein, the term “functionally-availablecyclodextrin” refers to cyclodextrin that is either not complexed withother materials (e.g. uncomplexed, free cyclodextrin) or is complexedwith materials that only weakly complex with cyclodextrin, e.g. weaklycomplexing materials that have a cyclodextrin complexation constant ofless than about 5,000 M⁻¹, preferably less than about 4,000 M⁻¹, andmore preferably less than about 3,000 M⁻¹. So long as the cyclodextrinin the present compositions is only complexed with weakly complexingmaterials, the cyclodextrin will still be available to complex withunwanted molecules on the surfaces to be treated. Since the unwantedmolecules will generally have a cyclodextrin complexation constant thatis higher than weakly complexing materials that might be contained inthe present compositions, the cyclodextrin will nevertheless beavailable to complex with the unwanted molecules due to the replacementof weakly complexing materials with the unwanted molecules in thecyclodextrin complexes in the present compositions.

[0022] The cavities within the functionally-available cyclodextrin inthe compositions of the present invention should remain essentiallyunfilled (i.e. the cyclodextrin remains uncomplexed and free) or filledwith only weakly complexing materials when in solution, in order toallow the cyclodextrin to absorb (i.e. complex with) various unwantedmolecules, such as malodor molecules, when the composition is applied toa surface containing the unwanted molecules. Non-derivatized (normal)beta-cyclodextrin can be present at a level up to its solubility limitof about 1.85% (about 1.85g in 100 grams of water) at room temperature.Beta-cyclodextrin is not preferred in compositions which call for alevel of cyclodextrin higher than its water solubility limit.Non-derivatized beta-cyclodextrin is generally not preferred when thecomposition contains surfactant since it affects the surface activity ofmost of the preferred surfactants that are compatible with thederivatized cyclodextrins.

[0023] The level of low-degree of substitution cyclodextrin derivativesthat are functionally-available in the present compositions is typicallyat least about 0.001%, preferably at least about 0.01%, and morepreferably at least about 0.1%, by weight of the composition. The totallevel of cyclodextrin in the present composition will be at least equalto or greater than the level of functionally-available cyclodextrin. Thelevel of functionally-available will typically be at least about 10%,preferably at least about 20%, and more preferably at least about 30%,by weight of the total level of cyclodextrin in the composition.

[0024] Concentrated compositions can also be used in order to deliver aless expensive product. When a concentrated product is used, i.e., whenthe total level of cyclodextrin used is from about 3% to about 60%, morepreferably from about 5% to about 40%, by weight of the concentratedcomposition, it is preferable to dilute the concentrated compositionbefore treating fabrics in order to avoid staining. Preferably theconcentrated cyclodextrin composition is diluted with about 50% to about6000%, more preferably with about 75% to about 2000%, most preferablywith about 100% to about 1000% by weight of the concentrated compositionof water. The resulting diluted compositions have usage concentrationsof total cyclodextrin and functionally-available cyclodextrin asdiscussed hereinbefore, e.g., of from about 0.1% to about 5%, by weightof the diluted composition of total cyclodextrin and usageconcentrations of functionally-available cyclodextrin of at least about0.001%, by weight of the diluted composition.

[0025] B. Optional Ingredients

[0026] 1. Carrier

[0027] The preferred carrier of the present invention is water. Thewater which is used can be distilled, deionized, or tap water. Water notonly serves as the liquid carrier for the cyclodextrins, but it alsofacilitates the complexation reaction between the cyclodextrin moleculesand any unwanted molecules on surfaces, such as malodorous moleculesthat are on inanimate surfaces such as fabric, when the surface istreated. It has been discovered that the intensity of unwantedmalodorous molecules generated by some polar, low molecular weightorganic amines, acids, and mercaptans is reduced when themalodor-contaminated surfaces are treated with an aqueous solution. Notto be bound by theory, it is believed that water solubilizes anddepresses the vapor pressure of these polar, low molecular weightorganic molecules, thus reducing their odor intensity.

[0028] The level of water in the present compositions can vary dependentupon the use of the composition. In compositions designed to be sprayedfrom manually or non-manually operated sprayers, the level of water ispreferably high, from about 30% to about 99.9%, more preferably fromabout 50% to about 99.5%, and still more preferably from about 60% toabout 95%.

[0029] Aqueous solutions that contain up to about 20% alochol,preferably up to about 10% alcohol, and more preferably up to about 5%alcohol, are preferred for odor controlling compositions for treatingfabrics. The dilute aqueous solution provides the maximum separation ofcyclodextrin molecules on the fabric and thereby maximizes the chancethat an odor molecule will interact with a cyclodextrin molecule.

[0030] 2. Cyclodextrin-compatible Surfactants

[0031] The stable compositions of the present invention for removing orreducing unwanted molecules preferably comprise cyclodextrin-compatiblesurfactants to form molecular aggregates with cyclodextrin-incompatiblematerials and to provide a low surface tension that permits thecomposition to spread more readily and more uniformly on hydrophobicsurfaces, like polyester and nylon. The spreading of the compositionalso allows it to dry faster, so that the treated material is ready touse sooner. Furthermore, the composition containing acyclodextrin-compatible surfactant can penetrate hydrophobic, oily soilbetter for improved reduction or removal of those types of unwantedmolecules. For the stable compositions of the present inventioncomprising functionally-available cyclodextrin, thecyclodextrin-compatible surfactant facilitates the formation of micellesor vesicles with many cyclodextrin-incompatible materials (e.g.cyclodextrin-incompatible surfactants, cyclodextrin-incompatibleenduring perfume materials, etc.), in order to preserve an effectiveamount of functionally-available cyclodextrin in the presentcompositions to reduce or remove unwanted molecules from the treatedsurfaces.

[0032] The surfactant for use in forming molecular aggregates withcyclodextrin-incompatible materials and in providing low surface tensionin the composition of the present invention should becyclodextrin-compatible, that is it should not substantially form acomplex with the cyclodextrin so as to diminish performance of thecyclodextrin and/or the surfactant. Complex formation diminishes boththe ability of the cyclodextrin to capture unwanted molecules,especially unwanted molecules, and the ability of the surfactant tolower the surface tension of the aqueous composition.

[0033] The important parameter in identifying cyclodextrin-compatiblesurfactants is its complexation constant with cyclodextrin, which is nogreater than about 5,000 M⁻¹, preferably no greater than about 4,000M⁻¹, and more preferably no greater than about 3,000 M-¹. Complexationconstants can be measured according to the Test Method describedhereinafter in Section IV.

[0034] Suitable cyclodextrin-compatible surfactants can also be readilyidentified by the absence of effect of cyclodextrin on the surfacetension provided by the surfactant. This is achieved by determining thesurface tension (in dyne/cm) of aqueous solutions of the surfactant inthe presence and in the absence of about 1% of a specific cyclodextrinin the solutions. The aqueous solutions contain surfactant atconcentrations of approximately 0.5%, 0.1%, 0.01%, and 0.005%. Thecyclodextrin can affect the surface activity of a surfactant byelevating the surface tension of the surfactant solution. If the surfacetension at a given concentration in water differs by more than about 10%from the surface tension of the same surfactant in the 1% solution ofthe cyclodextrin, that is an indication of a strong interaction betweenthe surfactant and the cyclodextrin. The preferred surfactants hereinshould have a surface tension in an aqueous solution that is different(lower) by less than about 10%, preferably less than about 5%, and morepreferably less than about 1% from that of the same concentrationsolution containing 1% cyclodextrin.

[0035] The cyclodextrin-compatible surfactants of the present inventionare either weakly interactive with cyclodextrin (less than 5% elevationin surface tension), or non-interactive (less than 1% elevation insurface tension). Typical surfactants like sodium dodecyl sulfate anddodecanolpoly(6)ethoxylate, which are cyclodextrin-incompatiblesurfactants, are strongly interactive, with more than a 10% elevation insurface tension in the presence of a typical cyclodextrin likehydroxypropyl beta-cyclodextrin and methylated beta-cyclodextrin.

[0036] Typical levels of cyclodextrin-compatible surfactants in usagecompositions are from about 0.01% to about 2%, preferably from about0.03% to about 0.6%, more preferably from about 0.05% to about 0.3%, byweight of the composition. Typical levels of cyclodextrin-compatiblesurfactants in concentrated compositions are from about 0.1% to about20%, preferably from about 0.2% to about 15%, more preferably from about0.3% to about 10%, by weight of the concentrated composition.

[0037] Useful cyclodextrin-compatible surfactants in the presentcompositions include, but are not limited to, cyclodextrin-compatiblesurfactants selected from the group consisting of: block copolymersurfactant, siloxane surfactant, anionic surfactant, castor oilsurfactant, sorbitan ester surfactant, polyethoxylated fatty alcoholsurfactant, glycerol mono-fatty acid ester surfactant, polyethyleneglycol fatty acid ester surfactant, fluorocarbon surfactant, andmixtures thereof. The cyclodextrin-compatible surfactants used in thepresent compositions are preferably selected from the group consistingof castor oil surfactant, sorbitan ester surfactant, polyethoxylatedfatty alcohol surfactant, glycerol mono-fatty acid ester surfactant,polyethylene glycol fatty acid ester surfactant, fluorocarbonsurfactant, and mixtures thereof.

[0038] a. Block Copolymer Surfactants

[0039] Nonlimiting examples of cyclodextrin-compatible nonionicsurfactants include block copolymers of ethylene oxide and propyleneoxide. Suitable block polyoxyethylene-polyoxypropylene polymericsurfactants, that are compatible with most cyclodextrins, include thosebased on ethylene glycol, propylene glycol, glycerol, trimethylolpropaneand ethylenediamine as the initial reactive hydrogen compound. Polymericcompounds made from a sequential ethoxylation and propoxylation ofinitial compounds with a single reactive hydrogen atom, such as C₁₂₋₁₈aliphatic alcohols, are not generally compatible with the cyclodextrin.Certain of the block polymer surfactant compounds designated Pluronic®and Tetronic® by the BASF-Wyandotte Corp., Wyandotte, Mich., are readilyavailable.

[0040] Nonlimiting examples of cyclodextrin-compatible surfactants ofthis type include:

[0041] Pluronic Surfactants with the general formulaH(EO)_(n)(PO)_(m)(EO)_(n)H,

[0042] wherein EO is an ethylene oxide group, PO is a propylene oxidegroup, and n and m are numbers that indicate the average number of thegroups in the surfactants. Typical examples of cyclodextrin-compatiblePluronic surfactants are: Name Average MW Average n Average m L-1013,800  4 59 L-81 2,750  3 42 L-44 2,200 10 23 L-43 1,850  6 22 F-384,700 43 16 P-84 4,200 19  43, and mixtures thereof.

[0043] Tetronic Surfactants with the general formula:

[0044] wherein EO, PO, n, and m have the same meanings as above. Typicalexamples of cyclodextrin-compatible Tetronic surfactants are: NameAverage MW Average n Average m 901  4,700  3 18 908 25,000 114  22,

[0045] and mixtures thereof.

[0046] “Reverse” Pluronic and Tetronic surfactants have the followinggeneral formulas:

[0047] Reverse Pluronic Surfactants H(PO)_(m)(EO)_(n)(PO)_(m)H

[0048] Reverse Tetronic Surfactants

[0049] wherein EO, PO, n, and m have the same meanings as above. Typicalexamples of cyclodextrin-compatible Reverse Pluronic and ReverseTetronic surfactants are:

[0050] Reverse Pluronic surfactants: Name Average MW Average n Average m10 R5 1,950  8 22 25 R1 2,700 21  6 Reverse Tetronic surfactants 130 R27,740  9 26 70 R2 3,870  4 13 and mixtures thereof.

[0051] b. Siloxane Surfactants

[0052] A preferred class of cyclodextrin-compatible nonionic surfactantsare the polyalkyleneoxide polysiloxanes having a dimethyl polysiloxanehydrophobic moiety and one or more hydrophilic polyalkylene side chainsand have the general formula:

R¹—(CH₃)₂SiO—[(CH₃)₂SiO]_(a)—[(CH₃)(R¹)SiO]_(b)—Si(CH₃)₂—R¹

[0053] wherein a+b are from about 1 to about 50, preferably from about 3to about 30 , more preferably from about 10 to about 25, and each R¹ isthe same or different and is selected from the group consisting ofmethyl and a poly(ethyleneoxide/propyleneoxide) copolymer group havingthe general formula:

—(CH₂)_(n)O(C₂H₄O)_(c)(C₃H₆O)_(d)R²

[0054] with at least one R¹ being a poly(ethyleneoxide/propyleneoxide)copolymer group, and wherein n is 3 or 4, preferably 3; total c (for allpolyalkyleneoxy side groups) has a value of from 1 to about 100,preferably from about 6 to about 100; total d is from 0 to about 14,preferably from 0 to about 3; and more preferably d is 0; total c+d hasa value of from about 5 to about 150, preferably from about 9 to about100 and each R² is the same or different and is selected from the groupconsisting of hydrogen, an alkyl having 1 to 4 carbon atoms, and anacetyl group, preferably hydrogen and methyl group.

[0055] Examples of this type of surfactants are the Silwet® surfactantswhich are available OSi Specialties, Inc., Danbury, Conn. RepresentativeSilwet surfactants are as follows. Name Average MW Average a + b Averagetotal c L-7608   600  1  9 L-7607 1,000  2 17 L-77   600  1  9 L-76056,000 20 99 L-7604 4,000 21 53 L-7600 4,000 11 68 L-7657 5,000 20 76L-7602 3,000 20 29

[0056] The molecular weight of the polyalkyleneoxy group (R¹) is lessthan or equal to about 10,000. Preferably, the molecular weight of thepolyalkyleneoxy group is less than or equal to about 8,000, and mostpreferably ranges from about 300 to about 5,000. Thus, the values of cand d can be those numbers which provide molecular weights within theseranges. However, the number of ethyleneoxy units (—C₂H₄O) in thepolyether chain (R¹) must be sufficient to render the polyalkyleneoxidepolysiloxane water dispersible or water soluble. If propyleneoxy groupsare present in the polyalkylenoxy chain, they can be distributedrandomly in the chain or exist as blocks. Preferred Silwet surfactantsare L-7600, L-7602, L-7604, L-7605, L-7657, and mixtures thereof.Besides surface activity, polyalkyleneoxide polysiloxane surfactants canalso provide other benefits, such as antistatic benefits, lubricity andsoftness to fabrics.

[0057] The preparation of polyalkyleneoxide polysiloxanes is well knownin the art. Polyalkyleneoxide polysiloxanes of the present invention canbe prepared according to the procedure set forth in U.S. Pat. No.3,299,112, incorporated herein by reference. Typically,polyalkyleneoxide polysiloxanes of the surfactant blend of the presentinvention are readily prepared by an addition reaction between ahydrosiloxane (i.e., a siloxane containing silicon-bonded hydrogen) andan alkenyl ether (e.g., a vinyl, allyl, or methallyl ether) of an alkoxyor hydroxy end-blocked polyalkylene oxide). The reaction conditionsemployed in addition reactions of this type are well known in the artand in general involve heating the reactants (e.g., at a temperature offrom about 85° C. to 1 10C) in the presence of a platinum catalyst(e.g., chloroplatinic acid) and a solvent (e.g., toluene).

[0058] c. Anionic Surfactants

[0059] Nonlimiting examples of cyclodextrin-compatible anionicsurfactants are the alkyldiphenyl oxide disulfonate, having the generalformula:

[0060] wherein R is an alkyl group. Examples of this type of surfactantsare available from the Dow Chemical Company under the trade name Dowfax®wherein R is a linear or branched C₆-C₁₆ alkyl group. An example ofthese cyclodextrin-compatible anionic surfactant is Dowfax 3B2 with Rbeing approximately a linear C₁₀ group. These anionic surfactants arepreferably not used when an antimicrobial active or preservative is usedwhich is cationic to minimize the interaction with the cationic actives,since the effect of both surfactant and active would be diminished.

[0061] d. Castor Oil Surfactants

[0062] The cyclodextrin-compatible surfactants useful in the presentinvention to form molecular aggregates, such as micelles or vesicles,with the cyclodextrin-incompatible materials of the present inventionfurther include polyoxyethylene castor oil ethers or polyoxyethylenehardened castor oil ethers or mixtures thereof, which are eitherpartially or fully hydrogenated. These ethoxylates have the followinggeneral formulae:

[0063] These ethoxylates can be used alone or in any mixture thereof.The average ethylene oxide addition mole number (.i.e., l+m+n+x+y+z inthe above formula) of these ethoxylates is generally from about 7 toabout 100, and preferably from about 20 to about 80. Castor oilsurfactants are commerically available from Nikko under the trade namesHCO 40 and HCO 60 and from BASF under the trade names Cremphor™ RH 40,RH 60, and CO 60.

[0064] e. Sorbitan Ester Surfactants

[0065] The sorbitan esters of long-chain fatty acids usable ascyclodextrin-compatible surfactants to form molecular aggregates withcyclodextrin-incompatible materials of the present invention includethose having long-chain fatty acid residues with 14 to 18 carbon atoms,desirably 16 to 18 carbon atoms. Furthermore, the esterification degreeof the sorbitan polyesters of long-chain fatty acids is desirably 2.5 to3.5, especially 2.8 to 3.2. Typical examples of these sorbitanpolyesters of long-chain fatty acids are sorbitan tripalmitate, sorbitantrioleate, and sorbitan tallow fatty acid triesters.

[0066] Other suitable sorbitan ester surfactants include sorbitan fattyacid esters, particularly the mono-and tri-esters of the formula:

[0067] and w is from about 10 to about 16.

[0068] Further suitable sorbitan ester surfactants includepolyethoxylated sorbitan fatty acid esters, particularly those of theformula:

[0069] u is from about 10 to about 16 and average (w+x+y+z) is fromabout 2 to about 20. Preferably, u is 16 and average (w+x+y+z) is fromabout 2 to about 4.

[0070] f. Polyethoxylated Fatty Alcohol Surfactants

[0071] Cyclodextrin-compatible surfactants further includepolyethoxylated fatty alcohol surfactants having the formula:

CH₃—(CH₂)_(x)—(CH═CH)_(y)—(CH₂)_(z)—(OCH₂CH₂)_(w)—OH

[0072] wherein w is from about 0 to about 100, preferably from about 0to about 80; y is 0 or 1; x is from about 1 to about 10; z is from about1 to about 10; x+z+y=11 to 25, preferably 11 to 23.

[0073] Branched (polyethoxylated) fatty alcohols having the followingformula are also suitable as cyclodextrin-compatible surfactants in thepresent compositions:

R—(OCH₂CH₂)_(w)—OH

[0074] wherein R is a branched alkyl group of from about 10 to about 26carbon atoms and w is as specified above.

[0075] g. Glycerol Mono-fatty Acid Ester Surfactants

[0076] Further cyclodextrin-compatible surfactants include glycerolmono-fatty acid esters, particularly glycerol mono-stearate, oleate,palmitate or laurate.

[0077] h. Polyethylene Glycol Fatty Acid Ester Surfactants

[0078] Fatty acid esters of polyethylene glycol, particularly those ofthe following formula, are cyclodextrin-compatible surfactants usefulherein:

R¹—(OCH₂CH₂)_(w)—OH

-or-

R¹—(OCH₂CH₂)_(w)—OR¹

[0079] wherein R¹ is a stearoyl, lauroyl, oleoyl or palmitoyl residue; wis from about 2 to about 20, preferably from about 2 to about 8.

[0080] i. Fluorocarbon Surfactants

[0081] Further cyclodextrin-compatible surfactants useful in the presentcompositions include fluorocarbon surfactants. Fluorocarbon surfactantsare a class of surfactants wherein the hydrophobic part of theamphiphile comprises at least in part some portion of a carbon-basedlinear or cyclic moiety having fluorines attached to the carbon wheretypically hydrogens would be attached to the carbons together with ahydrophilic head group. Some typical nonlimiting fluorocarbonsurfactants include fluorinated alkyl polyoxyalkylene, and fluorinatedalkyl esters as well as ionic surfactants. Representative structures forthese compounds are given below:

R_(f)R(R₁O)_(x)R₂  (1)

R_(f)R—OC(O)R₃  (2)

R_(f)R—Y—Z  (3)

R_(f)RZ  (4)

[0082] wherein R_(f) contains from about 6 to about 18 carbons eachhaving from about 0 to about 3 fluorines attached. R is either an alkylor alkylene oxide group which, when present, has from about 1 to about10 carbons and R₁ represents an alkylene radical having from about 1 toabout 4 carbons. R₂ is either a hydrogen or a small alkyl capping grouphaving from about 1 to about 3 carbons. R₃ represents a hydrocarbonmoiety comprising from about 2 to about 22 including the carbon on theester group. This hydrocarbon can be linear, branched or cyclicsaturated or unsaturated and contained moieties based on oxygen,nitrogen, and sulfur including, but not limited to ethers, alcohols,esters, carboxylates, amides, amines, thio-esters, and thiols; theseoxygen, nitrogen, and sulfur moieties can either interrupt thehydrocabon chain or be pendant on the hydrocarbon chain. In structure 3,Y represents a hydrocarbon group that can be an alkyl, pyridine group,amidopropyl, etc. that acts as a linking group between the fluorinatedchain and the hydrophilic head group. In structures 3 and 4, Zrepresents a cationic, anionic, and amphoteric hydrophilic head groupsincluding, but not limited to carboxylates, sulfates, sulfonates,quaternary ammonium groups, and betaines. Nonlimiting commerciallyavailable examples of these structures include Zonyl® 9075, FSO, FSN,FS-300, FS-310, FSN-100, FSO-100, FTS, TBC from DuPont and Fluorad™surfactants FC-430, FC-431, FC-740, FC-99, FC-120, FC-754, FC170C, andFC-171 from the 3M™ company in St. Paul, Minn.

[0083] 3. Water-soluble Polymers

[0084] Some water-soluble polymers, e.g., water-soluble cationic polymerand water-soluble anionic polymers can be used in the composition of thepresent invention to provide additional odor control benefits.

[0085] a. Cationic Polymers, e.g. Polyamines

[0086] Water-soluble cationic polymers, e.g., those containing aminofunctionalities, amido functionalities, and mixtures thereof, are usefulin the present invention to control certain acid-type odors.

[0087] b. Anionic Polymers, e.g., Polyacrylic Acid

[0088] Water-soluble anionic polymers, e.g., polyacrylic acids and theirwater-soluble salts are useful in the present invention to controlcertain amine-type odors. Preferred polyacrylic acids and their alkalimetal salts have an average molecular weight of less than about 20,000,more preferably less than 5,000. Polymers containing sulfonic acidgroups, phosphoric acid groups, phosphonic acid groups, and theirwater-soluble salts, and mixtures thereof, and mixtures with carboxylicacid and carboxylate groups, are also suitable.

[0089] Water-soluble polymers containing both cationic and anionicfunctionalities are also suitable. Examples of these polymers are givenin U.S. Pat. 4,909,986, issued March 20, 1990 to N. Kobayashi and A.Kawazoe, incorporated herein by reference. Another example ofwater-soluble polymers containing both cationic and anionicfunctionalities is a copolymer of dimethyldiallyl ammonium chloride andacrylic acid, commercially available under the trade name Merquat 280®from Calgon.

[0090] When a water-soluble polymer is used it is typically present at alevel of from about 0.001% to about 3%, preferably from about 0.005% toabout 2%, more preferably from about 0.01% to about 1%, and even morepreferably from about 0.05% to about 0.5%, by weight of the usagecomposition.

[0091] 4. Wrinkle Control Agents

[0092] The present compositions can optionally further comprise awrinkle control agent, wherein the wrinkle control agent is preferablycyclodextrin-compatible. Cyclodextrin-compatible wrinkle control agentsuseful herein include fiber lubricant, shape retention polymer,hydrophilic plasticizer, lithium salt, and mixtures thereof. Suchcyclodextrin-compatible wrinkle control agents are described in detailin U.S. Pat. No. 6,001,343 issued Dec. 14, 1999 to Trinh et al., whichis hereby incorporated by reference herein. Wrinkle control compositionsthat can be suitable as base compositions of the present invention thatcontain low-degree of substitution cyclodextrin-derivatives, especiallycompositions that can be used in a cabinet-type or bag-type apparatusfor conditioning garments, are also disclosed in InternationalApplication No. PCT/US98/08129, filed Apr. 27, 1998, and published Nov.4, 1999 as WO99/55950 by Hubesch et al. (P&G Case CM-1714); andInternational Application No. PCT/US98/08124, filed Apr. 27, 1998, andpublished Nov. 4, 1999 as WO99/55816 by Woo et al. (P&G Case 7097) whichare incorporated herein by reference.

[0093] 5. Cyclodextrin-incompatible Surfactants

[0094] Cyclodextrin-incompatible surfactants have a strong affinity forcomplexing with cyclodextrin, which has traditionally made it difficultto formulate compositions containing both functionally-availablecyclodextrin and cyclodextrin-incompatible materials.Cyclodextrin-incompatible surfactants typically have a complexationconstant of greater than about 5,000 M⁻¹, preferably greater than about8,000 M⁻¹, and more preferably greater than about 10,000 M⁻¹. However,Applicants have surprisingly found that compositions can be carefullyformulated, as described herein, to comprise bothcyclodextrin-incompatible materials and functionally-availablecyclodextrin.

[0095] Cyclodextrin-incompatible surfactants generally can be readilyidentified by the noticeable effect of cyclodextrin on the surfacetension provided by the cyclodextrin-incompatible surfactant. This isachieved by determining the surface tension (in dyne/cm) of aqueoussolutions of the cyclodextrin-incompatible surfactant in the presenceand in the absence of about 1% of a specific cyclodextrin in thesolutions. The aqueous solutions contain cyclodextrin-incompatiblesurfactant at concentrations of approximately 0.5%, 0.1%, 0.01%, and0.005%. The cyclodextrin can affect the surface activity of a surfactantby elevating the surface tension of the surfactant solution. If thesurface tension at a given concentration in water differs by more thanabout 10% from the surface tension of the same surfactant in the 1%solution of the cyclodextrin, that is an indication of a stronginteraction between the surfactant and the cyclodextrin, and identifiesthe surfactant as a cyclodextrin-incompatible surfactant. Thecyclodextrin-incompatible surfactants herein typically have a surfacetension in an aqueous solution that is different (lower) by at leastabout 10%, preferably at least about 13%, and more preferably at leastabout 15% from that of the same concentration solution containing 1%cyclodextrin.

[0096] When the cyclodextrin-incompatible surfactant is combined withother components (e.g. cyclodextrin-compatible surfactants) of thepresent compositions, before the addition of the cyclodextrin to formthe present compositions, the cyclodextrin-incompatible surfactant ismaintained in molecular aggregates such as micelles or vesicles in thecomposition matrix. The cyclodextrin-incompatible surfactants of thepresent invention generally have a critical micelle concentration(“CMC”) of at least about 10⁻⁴ mol/l, preferably at least about 10⁻³mol/l. When combined with other surfactants, such ascyclodextrin-compatible surfactants (as described hereinafter) having acomplexation constant of no greater than about 5,000 M⁻¹, preferably nogreater than about 4,000 M⁻¹, and more preferably no greater than about3,000 M⁻¹, the total CMC of the surfactant mixture of the presentcompositions is no greater than about 10⁻² mol/l, preferably no greaterthan about 10⁻³ mol/l, and more preferably no greater than about 10⁻⁴mol/l.

[0097] Examples of cyclodextrin-incompatible surfactants include anionicsurfactants, amphoteric surfactants, cationic surfactants, and mixturesthereof. Such surfactants are commonly used in detergent compositions,fabric softening compositions, shampoo compositions, hard surfacecleaning compositions, cosmetic compositions, personal carecompositions/bars, mouth rinse compositions, body wash compositions,shaving compositions, skin moisturizing compositions, and the like.

[0098] a. Anionic Surfactants

[0099] Anionic surfactants that tend to be cyclodextrin-incompatible andare useful herein include alkyl and alkyl ether sulfates. Thesematerials have the respective formulae ROSO₃M and RO(C₂HO)_(x)SO₃M,wherein R is alkyl or alkenyl of from about 8 to about 30 carbon atoms,x is 1 to about 10, and M is hydrogen or a cation such as ammonium,alkanolammonium (e.g., triethanolammonium), a monovalent metal cation(e.g., sodium and potassium), or a polyvalent metal cation (e.g.,magnesium and calcium). Preferably, M should be chosen such that theanionic surfactant component is water soluble. The anionic surfactant orsurfactants should be chosen such that the Krafft temperature is about15° C. or less, preferably about 10° C. or less, and more preferablyabout 0° C. or less. It is also preferred that the anionic surfactant besoluble in the composition hereof.

[0100] Krafft temperature refers to the point at which solubility of anionic surfactant becomes determined by crystal lattice energy and heatof hydration, and corresponds to a point at which solubility undergoes asharp, discontinuous increase with increasing temperature. Each type ofsurfactant will have its own characteristic Krafft temperature. Kraffttemperature for ionic surfactants is, in general, well known andunderstood in the art. See, for example, Myers, D., Surfactant Scienceand Technology, pp. 82-85, VCH Publishers, Inc. (New York, N.Y., USA),1988 (ISBN 0-89573-399-0), which is incorporated by reference herein inits entirety.

[0101] In the alkyl and alkyl ether sulfates described above, R can havefrom about 12 to about 18 carbon atoms in both the alkyl and alkyl ethersulfates. The alkyl ether sulfates are typically made as condensationproducts of ethylene oxide and monohydric alcohols having from about 8to about 24 carbon atoms. The alcohols can be derived from fats, e.g.,coconut oil, palm oil, tallow, or the like, or the alcohols can besynthetic. Lauryl alcohol and straight chain alcohols derived fromcoconut oil and palm oil are useful herein. Such alcohols are reactedwith 1 to about 10, and especially about 3, molar proportions ofethylene oxide and the resulting mixture of molecular species having,for example, an average of 3 moles of ethylene oxide per mole ofalcohol, is sulfated and neutralized.

[0102] Specific examples of alkyl ether sulfates which can be used inthe present invention as cyclodextrin-incompatible surfactants aresodium and ammonium salts of coconut alkyl triethylene glycol ethersulfate; tallow alkyl triethylene glycol ether sulfate, and tallow alkylhexaoxyethylene sulfate. Highly preferred alkyl ether sulfates are thosecomprising a mixture of individual compounds, said mixture having anaverage alkyl chain length of from about 12 to about 16 carbon atoms andan average degree of ethoxylation of from 1 to about 4 moles of ethyleneoxide. Such a mixture also comprises from 0% to about 20% by weightC₁₂₋₁₃ compounds; from about 60% to about 100% by weight of C₁₄₋₁₆compounds, from 0% to about 20% by weight of C₁₇₋₁₉ compounds; fromabout 3% to about 30% by weight of compounds having a degree ofethoxylation of 0; from about 45% to about 90% by weight of compoundshaving a degree of ethoxylation of from 1 to about 4; from about 10% toabout 25% by weight of compounds having a degree of ethoxylation of fromabout 4 to about 8; and from about 0.1% to about 15% by weight ofcompounds having a degree of ethoxylation greater than about 8.

[0103] Other anionic surfactants that tend to becyclodextrin-incompatible are the water-soluble salts of organic,sulfuric acid reaction products of the general formula [R₁—SO₃—M] whereR₁ is selected from the group consisting of a straight or branchedchain, saturated aliphatic hydrocarbon radical having from about 8 toabout 24, preferably about 10 to about 18, carbon atoms; and M is aspreviously described above in this section. Examples of such surfactantsare the salts of an organic sulfuric acid reaction product of ahydrocarbon of the methane series, including iso-, neo-, andn-paraffins, having about 8 to about 24 carbon atoms, preferably about12 to about 18 carbon atoms and a sulfonating agent, e.g., SO₃, H₂SO₄,obtained according to known sulfonation methods, including bleaching andhydrolysis. Preferred are alkali metal and ammonium sulfonated C₁₀₋₁₈n-paraffins.

[0104] Still other anionic surfactants that tend to becyclodextrin-incompatible are the reaction products of fatty acidsesterified with isethionic acid and neutralized with sodium hydroxidewhere, for example, the fatty acids are derived from coconut or palmoil; or sodium or potassium salts of fatty acid amides of methyl tauridein which the fatty acids, for example, are derived from coconut oil.Other similar anionic surfactants are described in U.S. Pat. Nos.2,486,921, 2,486,922, and 2,396,278, which are incoproated by referenceherein in their entirety.

[0105] Still other useful anionic surfactants that tend to becyclodextrin-incompatible are those that are derived from taurine, whichis also known as 2-aminoethanesulfonic acid. An example of such an acidis N-acyl-N-methyl taurate.

[0106] Other anionic surfactants that tend to becyclodextrin-incompatible and are suitable for use in the presentcompositions are the succinates, examples of which include disodiumN-octadecylsulfosuccinate; disodium lauryl sulfosuccinate; diammoniumlauryl sulfosuccinate; tetrasodiumN-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinate; the diamyl ester ofsodium sulfosuccinic acid; the dihexyl ester of sodium sulfosuccinicacid; and the dioctyl ester of sodium sulfosuccinic acid.

[0107] Other suitable anionic surfactants include olefin sulfonateshaving about 10 to about 24 carbon atoms. The term “olefin sulfonates”is used herein to mean compounds which can be produced by thesuffonation of alpha-olefins by means of uncomplexed sulflr trioxide,followed by neutralization of the acid reaction mixture in conditionssuch that any sulfones which have been formed in the reaction arehydrolyzed to give the corresponding hydroxyalkanesulfonates. The sulfurtrioxide can be liquid or gaseous, and is usually, but not necessarily,diluted by inert diluents, for example by liquid SO₂, chlorinatedhydrocarbons, etc., when used in the liquid form, or by air, nitrogen,gaseous SO₂, etc., when used in the gaseous form.

[0108] The alpha-olefins from which the olefin sulfonates are derivedare mono-olefins having about 12 to about 24 carbon atoms, preferablyabout 14 to about 16 carbon atoms. Preferably, they are straight chainolefins.

[0109] In addition to the true alkene sulfonates and a proportion ofhydroxy-alkanesulfonates, the olefin sulfonates can contain minoramounts of other materials, such as alkene disulfonates depending uponthe reaction conditions, proportion of reactants, the nature of thestarting olefins and impurities in the olefin stock and side reactionsduring the sulfonation process. A specific alpha-olefin sulfonatemixture of the above type is described more fully in U.S. Pat. No.3,332,880, to Pflaumer and Kessler, issued Jul. 25, 1967, which isincorporated by reference herein in its entirety.

[0110] Another class of anionic surfactants that tend to becyclodextrin-incompatible and are suitable for use in the presentcompositions are the beta-alkyloxy alkane sulfonates. These compoundshave the following formula:

[0111] where R¹ is a straight chain alkyl group having from about 6 toabout 20 carbon atoms, R² is a lower allyl group having from about 1,preferred, to about 3 carbon atoms, and M is as hereinbefore described.

[0112] Many other anionic surfactants that tend to becyclodextrin-incompatible and are suitable for use in the presentcompositions are described in McCutcheon's, Emulsifiers and Detergents,1989 Annual, published by M. C. Publishing Co., and in U.S. Pat. No.3,929,678, which descriptions are incorporated herein by reference intheir entirety.

[0113] Examples of anionic surfactants that tend to becyclodextrin-incompatible and useful in detergent compositions and/orshampoo compositions herein include ammonium lauryl sulfate, ammoniumlaureth sulfate, triethylamine lauryl sulfate, triethylamine laurethsulfate, triethanolamine lauryl sulfate, triethanolamine laurethsulfate, monoethanolamine lauryl sulfate, monoethanolamine laurethsulfate, diethanolamine lauryl sulfate, diethanolamine laureth sulfate,lauric monoglyceride sodium sulfate, sodium lauryl sulfate, sodiumlaureth sulfate, potassium lauryl sulfate, potassium laureth sulfate,ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodium cocoylsulfate, sodium lauroyl sulfate, potassium cocoyl sulfate, potassiumlauryl sulfate, triethanolamine lauryl sulfate, triethanolamine laurylsulfate, monoethanolamine cocoyl sulfate, monoethanolamine laurylsulfate, sodium N-lauroyl-N-methyl taurate, sodium tridecyl benzenesulfonate, and sodium dodecyl benzene sulfonate. Preferred for useherein are detersive anionic surfactants selected from the groupconsisting of ammonium laureth-3 sulfate, sodium alureth-3 sulfate,ammonium lauryl sulfate, sodium lauryl sulfate, and mixtures thereof.

[0114] b. Amphoteric Surfactants

[0115] The cyclodextrin-incompatible surfactants of the presentinvention can also include amphoteric surfactants. The term “amphotericsurfactant,” as used herein, is also intended to encompass zwitterionicsurfactants, which are well known to formulators skilled in the art as asubset of amphoteric surfactants. A wide variety of amphotericsurfactants tend to be cyclodextrin-incompatible and can be incorporatedin the compositions of the present invention containingfunctionally-available cyclodextrin. Particularly useful amphotericsurfactants are those which are broadly described as derivatives ofaliphatic secondary and tertiary amines, preferably wherein the nitrogenis in a cationic state, in which the aliphatic radicals can be straightor branched chain and wherein one of the radicals contains an ionizablewater solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate,or phosphonate.

[0116] Nonlimiting examples of amphoteric surfactants that tend to becyclodextrin-incompatible and are useful in the compositions of thepresent invention are disclosed in McCutcheon's, Detergents andEmulsifiers, North American edition (1986), published by alluredPublishing Corporation; and McCutcheon's, Functional Materials, NorthAmerican Edition (1992); both of which are incorporated by referenceherein in their entirety.

[0117] Examples of amphoteric or zwitterionic surfactants include thebetaines, sultaines, and hydroxysultaines. Examples of betaines includethe higher alkyl betaines, such as coco dimethyl carboxymethyl betaine,lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alphacarboxyethylbetaine, cetyl dimethyl carboxymethyl betaine, cetyl dimethyl betaine(available as Lonzaine 16SP from Lonza Corp.), laurylbis-(2-hydroxyethyl) carboxymethyl betaine, stearylbis-(2-hydroxypropyl) carboxymethyl betaine, oleyl d-methylgamma-carboxypropyl betaine, laurylbis-(2-hydroxypropyl)alpha-carboxyethyl betaine, coco dimethylsulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, stearylbetaine, lauryl dimethyl sulfoethyl betaine, lauryl bis-(2-hydroxyethyl)sulfopropyl betaine, and amidobetaines and amidosulfobetaines (whereinthe RCONH(CH₂)₃ radical is attached to the nitrogen atom of thebetaine), oleyl betaine (available as amphoteric Velvetex OLB-50 fromHenkel), and cocamidopropyl betaine (available as Velvetex BK-35 andBA-35 from Henkel).

[0118] Examples of sultaines and hydroxysultaines include materials suchas cocamidopropyl hydroxysultaine (available as Mirataine CBS from RhonePoulenc).

[0119] Suitable amphoteric surfactants that tend to becyclodextrin-incompatible have the following structure:

[0120] wherein R¹ is unsubstituted, saturated or unsaturated, straightor branched chain alkyl having from about 9 to about 22 carbon atoms.Preferred R¹ has from about 11 to about 18 carbon atoms; more preferablyfrom about 12 to about 18 carbon atoms; more preferably still from about14 to about 18 carbon atoms; m is an integer from 1 to about 3, morepreferably from about 2 to about 3, and more preferably about 3; n iseither 0 or 1, preferably 1; R² and R³ are independently selected fromthe group consisting of alkyl having from 1 to about 3 carbon atoms,unsubstituted or mono-substituted with hydroxy, preferred R² and R³ areCH₃ ; X is selected from the group consisting of CO₂, SO₃ and SO₄; R⁴ isselected from the group consisting of saturated or unsaturated, straightor branched chain allyl, unsubstituted or monosubstituted with hydroxy,having from 1 to about 5 carbon atoms. When X is CO₂, R⁴ preferably has1 or 3 carbon atoms, more preferably 1 carbon atom. When X is SO₃ orSO₄, R⁴ preferably has from about 2 to about 4 carbon atoms, morepreferably 3 carbon atoms.

[0121] Examples of amphoteric surfactants of the present inventioninclude the following compounds: cetyl dimethyl betaine;cocamidopropylbetaine (wherein the alkyl group has from about 9 to about13 carbon atoms); cocamidopropyl hydroxy sultaine (wherein the alkylgroup has from about 9 to about 13 carbon atoms); stearyl dimethylbetaine; and behenyl dimethyl betaine.

[0122] Other amphoteric surfactants of the present invention that tendto be cyclodextrin-incompatible include cetyl dimethyl betaine,cocamidopropyl betaine, stearyl dimethyl betaine, and cocamidopropylhydroxy sultaine.

[0123] Examples of other useful amphoteric surfactants that tend to becyclodextrin- incompatible are alkyliminoacetates, and iminodialkanoatesand aminoalkanoates of the formulas RN[(CH₂)_(m)CO₂M]₂ andRNH(CH₂)_(m)CO₂M wherein m is from 1 to 4, R is a C₈-C₂₂ alkyl oralkenyl, and M is H, alkali metal, alkaline earth metal ammonium, oralkanolammonium. Also included are imidazolinium and ammoniumderivatives. Other examples of useful amphoterics include phosphates,such as cocamidopropyl PG-dimonium chloride phosphate (commerciallyavailable as Monaquat PTC, from Mona Corp.).

[0124] The cyclodextrin-incompatible surfactant of the compositions ofthe present invention can also include amino acid derivativesurfactants. By amino acid derivative, as defined herein, is meant asurfactant that has the basic chemical structure of an amino acidcompound, i.e. that contains a structural component of one of thenaturally-occurring amino acids. Common amino acids from which suchsurfactants are derived include glycine, N-methyl glycine which is alsoknown as sarcosine, glutamic acid, arginine, alanine, phenylalanine, andthe like. Other surfactants suitable for use in the present compositionsare those that are derived from amino acids. Also useful herein aresalts of these amino acid derived surfactants. Nonlimiting examples ofsuch surfactants include N-acyl-L-glutamate; N-acyl-N-methyl-β-alanate;N-acylsarcosinate; N-alkylamino-propionates andN-alkyliminodipropionates specific examples of which includeN-lauryl-β-amino propionic acid or salts thereof, andN-lauryl-β-imino-dipropionic acid; sodium lauryl sarcosinate, sodiumlauroyl sarcosinate, lauryl sarcosine, cocoyl sarcosine, and mixturesthereof.

[0125] c. Cationic Surfactants

[0126] Cationic surfactants typically contain quaternary nitrogenmoieties and tend to be cyclodextrin-incompatible. Cationic surfactantsamong those useful herein are disclosed in the following documents, allof which are incorporated by reference herein in their entirety: M.C.Publishing Co., McCutcheon's, Detergents & Emulsifiers, (North Americanedition 1979); Schwartz, et al., Surface Active Agents, Their Chemistryand Technology, New York: Interscience Publishers, 1949; U.S. Pat. No.3,155,591, Hilfer, issued Nov. 3, 1964; U.S. Pat. No. 3,929,678,Laughlin et al., issued Dec. 30, 1975; U.S. Pat. No. 3,959,461, Baileyet al., issued May 25, 1976; and U. S. Pat. No. 4,387,090, Bolich, Jr.,issued Jun. 7, 1983.

[0127] Among the cationic surfactant materials that tend to becyclodextrin-incompatible and are useful herein are those correspondingto the general formula:

[0128] wherein R¹, R², R³, and R⁴ are independently selected from analiphatic group of from 1 to about 22 carbon atoms or an aromatic,alkoxy, polyoxyalkylene, alkylamnido, hydroxyalkyl, aryl or alkylarylgroup having up to about 22 carbon atoms; and X is a salt-forming anionsuch as those selected from halogen, (e.g. chloride, bromide), acetate,citrate, lactate, glycolate, phosphate nitrate, sulfate, andalkylsulfate radicals. The aliphatic groups can contain, in addition tocarbon and hydrogen atoms, ether linkages, and other groups such asamino groups. The longer chain aliphatic groups, e.g., those of about 12carbons, or higher, can be saturated or unsaturated. Preferred is whenR¹, R², R³, and R⁴ are independently selected from C₁ to about C₂₂alkyl. Especially preferred are cationic materials containing two longalkyl chains and two short alkyl chains or those containing one longalkyl chain and three short alkyl chains. The long alkyl chains in thecompounds described in the previous sentence have from about 12 to about22 carbon atoms, preferably from about 16 to about 22 carbon atoms, andthe short alkyl chains in the compounds described in the previoussentence have from 1 to about 3 carbon atoms, preferably from 1 to about2 carbon atoms.

[0129] Also preferred are cationic materials in which at least one ofthe substituents is selected from hydroxyalkyl, preferably hydroxyethylor hydroxy propyl, or polyoxyalkylene, preferably polyoxyethylene orpolyoxypropylene wherein the total degree of ethoxylation orpropoxylation in the molecule is from about 5 to about 20. Nonlimitingexamples of commercially available materials include Variquat K1215 and638 from Witco Chemical, Dehyquat SP from Henkel, and Atlas G265 fromICI Americas.

[0130] Other cationic materials that tend to becyclodextrin-incompatible include the materials having the followingCTFA designations: quaternium-8, quaternium-24, quaternium-26,quaternium-27, quaternium-30, quaternium-33, quaternium-43,quaternium-52, quaternium-53, quaternium-56, quaternium-60,quaternium-62, quaternium-70, quaternium-72, quaternium-75,quaternium-77, quaternium-78, quaternium-79, quaternium-80,quaternium-81, quaternium-82, quaternium-83, quaternium-84, and mixturesthereof.

[0131] Salts of primary, secondary and tertiary fatty amines are alsosuitable cationic surfactant materials. The alkyl groups of such aminespreferably have from about 12 to about 22 carbon atoms, and can besubstituted or unsubstituted. Such amines, useful herein, includestearamido propyl dimethyl amine, diethyl amino ethyl stearamide,dimethyl stearamine, dimethyl soyamine, soyamine, myristyl amine,tridecyl amine, ethyl stearylamine, N-tallowpropane diamine, ethoxylated(with 5 moles of ethylene oxide) stearylamine, dihydroxy ethylstearylamine, and arachidylbehenylamine. Suitable amine salts includethe halogen, acetate, phosphate, nitrate, citrate, lactate, and alkylsulfate salts. Such salts include stearylamine hydrochloride, soyaminechloride, stearylamine formate, N-tallowpropane diamine dichloride andstearamidopropyl dimethylamine citrate. Cationic amine surfactantsincluded among those useful in the present invention are disclosed inU.S. Pat. No. 4,275,055, Nachtigal, et al., issued Jun. 23, 1981, whichis incorporated by reference herein in its entirety.

[0132] The following Table provides non-liiting examples ofcyclodextrin-incompatible surfactants of the present invention, alongwith their respective complexation constants with cyclodextrin.

Examples of Cyclodextrin-Incompatible Surfactants

[0133] CD incompatible surfactant Complexation Constant (K) Sodiumdodecyl sulfate about 22000 Sodium laurate about 16000 Lauramine oxideabout 7500  Dodecyltrimethylammonium bromide about 18100 Cetylpyridinium chloride about 48000 Laureth-6 about 10000

[0134] 6. Cyclodextrin-incompatible Perfume Materials

[0135] The stable compositions of the present invention preferablyprovide a “scent signal” in the form of a pleasant odor which imparts afreshness impression to the treated surface and can serve as a signal ofthe capturing of the unwanted molecules, e.g. malodorous molecules, fromthe treated surfaces, such as fabrics. The cyclodextrin-incompatibleperfume materials herein are designed to provide, at least in part, alasting perfume scent. Perfume is added at levels of from about 0% toabout 3%, preferably from about 0.003% to about 2%, more preferably fromabout 0.005% to about 1%, by weight of the usage composition.

[0136] Perfume can be added to provide a more lasting odor on thetreated surfaces. When stronger levels of perfume are preferred,relatively higher levels of perfume can be added. Any type of perfumecan be incorporated into the compositions of the present invention solong as the enduring hydrophobic perfume materials that arecyclodextrin-incompatible are properly incorporated in the presentcompositions such that functionally-available cyclodextrin remains inthe compositions at the requisite levels. The perfume ingredients can beeither hydrophilic or hydrophobic. The cyclodextrin-incompatible perfumematerials of the present invention have complexation constants withcyclodextrin of greater than about 5,000 M⁻¹, preferably greater thanabout 8,000 M⁻¹, and more preferably greater than about 10,000 M⁻¹.

[0137] In order to provide long lasting effects, the perfume is at leastpartially hydrophobic and has a relatively high boiling point. I.e., theperfume is composed predominantly of perfume materials selected from twogroups of ingredients, namely, (a) hydrophobic ingredients (i.e.generally cyclodextrin-incompatible perfume materials) having a ClogP ofmore than about 3, more preferably more than about 3.5, and (b)ingredients having a molecular weight above about 210, preferably aboveabout 220. Typically, at least about 50%, preferably at least about 60%,more preferably at least about 70%, and most preferably at least about80% by weight of the perfume is composed of cyclodextrin-incompatibleenduring perfume materials of the above groups (a) and (b). For thesepreferred perfumes, the total cyclodextrin to perfume weight ratio istypically of from about 2:1 to about 200:1; preferably from about 4:1 toabout 100:1, more preferably from about 6:1 to about 50:1, and even morepreferably from about 8:1 to about 30:1.

[0138] Hydrophobic perfume materials have a tendency to strongly complexwith the cyclodextrins, thus being cyclodextrin-incompatible. The degreeof hydrophobicity of a perfume ingredient can be correlated with itsoctanol/water partition coefficient P. The octanol/water partitioncoefficient of a perfume ingredient is the ratio between its equilibriumconcentration in octanol and in water. A perfume ingredient with agreater partition coefficient P is considered to be more hydrophobic.Conversely, a perfume ingredient with a smaller partition coefficient Pis considered to be more hydrophilic. Since the partition coefficientsof the perfume ingredients normally have high values, they are moreconveniently given in the form of their logarithm to the base 10, logP.Thus the cyclodextrin-incompatible enduring perfume materials of thisinvention have logP of about 3 or higher, preferably of about 3.5 orhigher.

[0139] The logP of many perfume ingredients have been reported in; forexample, the Pomona92 database, available from Daylight ChemicalInformation Systems, Inc. (Daylight CIS), Irvine, California, containsmany, along with citations to the original literature. However, the logPvalues are most conveniently calculated by the “CLOGP” program, alsoavailable from Daylight CIS. This program also lists experimental logPvalues when they are available in the Pomona92 database. The “calculatedlogP” (ClogP) is determined by the fragment approach of Hansch and Leo(cf., A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch,P. G. Sammens, J. B. Taylor and C. A. Ramsden, Eds., p. 295, PergamonPress, 1990, incorporated herein by reference). The fragment approach isbased on the chemical structure of each perfume ingredient, and takesinto account the numbers and types of atoms, the atom connectivity, andchemical bonding. The ClogP values, which are the most reliable andwidely used estimates for this physicochemical property, are usedinstead of the experimental logP values in the selection of perfumeingredients which are useful in the present invention.

[0140] Non-limiting examples of the cyclodextrin-incompatible enduring(hydrophobic) perfume materials are selected from the group consistingof: diethyl phthalate, methyl dihydro jasmonate, lyral, hexylsalicylate, iso-E super, hexyl cinnamic aldehyde, iso-propyl myristate,galaxolide, phenyl-ethyl-phenyl acetate, cis-jasmone; dimethyl benzylcarbinyl acetate; ethyl vanillin; geranyl acetate; alpha-ionone;beta-ionone; gamma-ionone; lauric aldehyde; methyl dihydrojasmonate;methyl nonyl acetaldehyde; gamma-nonalactone; phenoxy ethyliso-butyrate; phenyl ethyl dimethyl carbinol; phenyl ethyl dimethylcarbinyl acetate; alpha-methyl-4-(2-methylpropyl)-benzenepropanal(Suzaral T); 6-acetyl-1,1,3,4,4,6-hexamethyl tetrahydronaphthalene(Tonalid); undecylenic aldehyde; vanillin;2,5,5-trimethyl-2-pentylcyclopentanone (veloutone);2-tert-butylcyclohexanol (verdol); verdox; para-tert-butylcyclohexylacetate (vertenex); and mixtures thereof. Enduring perfume compositionscan be formulated using these cyclodextrin-incompatible enduring perfumematerials, preferably at a level of at least about 5%, more preferablyat least about 10%, and even more preferably at least about 20%, byweight of the perfume composition, the total level of enduring perfumeingredients, as disclosed herein, being at least about 70%, all byweight of said enduring perfume composition.

[0141] Other cyclodextrin-incompatible enduring perfume materials thatcan be used with the above named enduring perfume ingredients can becharacterized by boiling point (B.P.) and octanol/water partitioningcoefficient (P). The octanol/water partitioning coefficient of a perfumeingredient is the ratio between its equilibrium concentrations inoctanol and in water. These other enduring perfume ingredients of thisinvention have a molecular weight of more than about 210, preferablymore than about 220; and an octanol/water partitioning coefficient P ofabout 1,000 or higher. Since the partitioning coefficients of theseother enduring perfume ingredients of this invention have high values,they are more conveniently given in the form of their logarithm to thebase 10, logP. Thus these other enduring perfume ingredients of thisinvention have logP of about 3 or higher, preferably more than about3.1, and even more preferably more than about 3.2.

[0142] The following table illustrates the molecular weight property ofsome of the cyclodextrin-incompatible enduring (hydrophobic) perfumematerials (i.e. having significant or strong CD interaction) versuscyclodextrin-compatible perfume materials (i.e. having weak CDinteraction).

Examples of Perfume Components for CD Interaction

[0143] Perfume component Molecular weight CD interaction DiethylPhthalate 222.0 weak Methyl Dihydro Jasmonate 226.3 weak Lyral 210.3weak Hexyl Salicylate 222.3 weak Iso-E Super 234.0 weak Hexyl cinnamicAldehyde 216.3 weak Iso-propyl Myristate 270.0 weak Galaxolide 258 weakTonalid 258 weak Phenyl-Ethyl-Phenyl Acetate 240 weak Tetrahydrolinalol158.0 significant Koavone 182.0 strong Terpinyl Acetate 196.0significant Vertenex 198.3 strong Flor Acetate 192.0 strong a-ionone192.3 strong Cymal 170.0 strong a-Me Ionone 206.3 strong Frutene 206.0strong Lilial 204.3 strong

[0144] Nonlimiting examples of other enduring (hydrophobic) perfumematerials which tend to be cyclodextrin-incompatible and can be used inthe perfume compositions of the present invention are:

Examples of Other Cyclodextrin-Incompatible Enduring Perfume Materials

[0145] Perfume Ingredients Approximate BP ≧ 250° C. and ClogP ≧ 3.0 B.P.(° C. (a) ClogP Allyl cyclohexane propionate   267 3.935 Ambrettolide  300 6.261 Ambrox DL (Dodecahydro-3a,6,6,9a-   250 5.400tetramethyl-naphtho[2,1-b]furan) Amyl benzoate   262 3.417 Amylcinnamate   310 3.771 Amyl cinnamic aldehyde   285 4.324 Amyl cinnamicaldehyde dimethyl acetal   300 4.033 iso-Amyl salicylate   277 4.601Aurantiol   450 4.216 Benzophenone   306 3.120 Benzyl salicylate   3004.383 para-tert-Butyl cyclohexyl acetate +250 4.019 iso-Butyl quinoline  252 4.193 beta-Caryophyllene   256 6.333 Cadinene   275 7.346 Cedrol  291 4.530 Cedryl acetate   303 5.436 Cedryl formate +250 5.070Cinnamyl cinnamate   370 5.480 Cyclohexyl salicylate   304 5.265Cyclamen aldehyde   270 3.680 Dihydro isojasmonate +300 3.009 Diphenylmethane   262 4.059 Diphenyl oxide   252 4.240 Dodecalactone   258 4.359iso E super +250 3.455 Ethylene brassylate   332 4.554 Ethyl methylphenyl glycidate   260 3.165 Ethyl undecylenate   264 4.888 Exaltolide  280 5.346 Galaxolide +250 5.482 Geranyl anthranilate   312 4.216Geranyl phenyl acetate +250 5.233 Hexadecanolide   294 6.805 Hexenylsalicylate   271 4.716 Hexyl cinnamic aldehyde   305 5.473 Hexylsalicylate   290 5.260 alpha-Irone   250 3.820 Lilial (p-t-bucinal)  258 3.858 Linalyl beuzoate   263 5.233 2-Methoxy naphthalene   2743.235 ganima-n-Methyl ionone   252 4.309 Musk indanone +250 5.458 Muskketone MP = 137° C. 3.014 Musk tibetine MP = 136° C. 3.831 Myristicin  276 3.200 Oxahexadecanolide-10 +300 4.336 Oxahexadecanolide-11 MP =35° C. 4.336 Patchouli alcohol   285 4.530 Phantolide   288 5.977 Phenylethyl benzoate   300 4.058 Phenyl ethyl phenyl acetate   325 3.767Phenyl heptanol   261 3.478 Phenyl hexanol   258 3.299 alpha-Santalol  301 3.800 Thibetolide   280 6.246 delta-Undecalactone   290 3.830gamma-Undecalactone   297 4.140 Undecavertol (4-methyl-3-decen-5-ol)  250 3.690 Vetiveryl acetate   285 4.882 Yara-yara   274 3.235 Ylangene  250 6.268

[0146] The preferred perfume compositions used in the present inventiontypically contain at least 4 different cyclodextrin-incompatibleenduring (hydrophobic) perfume materials, preferably at least 5different cyclodextrin-incompatible enduring (hydrophobic) perfumematerials, more preferably at least 6 differentcyclodextrin-incompatible enduring (hydrophobic) perfume materials, andeven more preferably at least 7 different cyclodextrin-incompatibleenduring (hydrophobic) perfume materials. Most common perfume materialswhich are derived from natural sources are composed of a multitude ofcomponents. When each such material is used in the formulation of thepreferred perfume compositions of the present invention, it is countedas one single material, for the purpose of defining the invention.

[0147] In order to allow for functionally-available cyclodextrin in thepresent compositions, the cyclodextrin-incompatible enduring(hydrophobic) perfume materials are preferably processed with othercomponents before the addition of cyclodextrin as described hereinafterin Section II.

[0148] 7. Cyclodextrin-compatible Perfume Materials

[0149] Hydrophilic perfume materials tend to be cyclodextrin-compatiblein aqueous compositions. Cyclodextrin-compatible perfume materials havecomplexation constants with cyclodextrin of no greater than about 5,000M⁻¹, preferably no greater than about 4,000 M⁻¹, and more preferably nogreater than about 3,000 M⁻¹. Hydrophilic perfumes are composedpredominantly of ingredients having a ClogP, as described hereinbefore,of less than about 3.5, more preferably less than about 3.0. If theperfume ingredients are hydrophilic, they should be dissolved in theaqueous phase so they do not complex with the cyclodextrin. It isimportant to note that for best product stability and improvedcyclodextrin compatibility and to maintain functionally-availablecyclodextrin, a clear premix consisting of hydrophilic perfumeingredients, cyclodextrin compatible surfactant, and solubility aid (forexample, ethanol) is firstly made so that all hydrophilic perfumeingredients are pre-dissolved. Cyclodextrin, water hold and optionalingredients are always added during the final mixing stage. In order toreserve an effective amount of functionally-available cyclodextrin forreducing/removing unwanted molecules, such as malodorous molecules,hydrophilic perfume ingredients are typically present at a level whereinless than about 90% of the cyclodextrin complexes with the perfume,preferably less than about 50% of the cyclodextrin complexes with theperfume, more preferably, less than about 30% of the cyclodextrincomplexes with the perfume, and most preferably, less than about 10% ofthe cyclodextrin complexes with the perfume. The cyclodextrin to perfumeweight ratio is preferably greater than about 8:1, more preferablygreater than about 10:1, still more preferably greater than about 20:1,even more preferably greater than 40:1 and most preferably greater thanabout 70:1.

[0150] 8. Cyclodextrin-compatible Antimicrobial Actives

[0151] A solubilized, water-soluble, cyclodextrin-compatibleantimicrobial active, is useful in the present compositions forproviding protection against organisms that become attached to thetreated material. The antimicrobial should be cyclodextrin-compatible,e.g., not substantially forming complexes with the cyclodextrin in thestable compositions of the present invention. The free, uncomplexedantimicrobial, e.g., antibacterial, active provides an optimumantibacterial performance.

[0152] Sanitization of fabrics can be achieved by the compositions ofthe present invention containing, antimicrobial materials, e.g.,antibacterial halogenated compounds, quaternary compounds, and phenoliccompounds.

[0153] Biguanides.

[0154] Some of the more robust cyclodextrin-compatible antimicrobialhalogenated compounds which can function as disinfectants/sanitizers aswell as finish product preservatives (vide infra), and are useful in thecompositions of the present invention include 1,1′-hexamethylenebis(5-(p-chlorophenyl)biguanide), commonly known as chlorhexidine, andits salts, e.g., with hydrochloric, acetic and gluconic acids. Thedigluconate salt is highly water-soluble, about 70% in water, and thediacetate salt has a solubility of about 1.8% in water. Whenchlorhexidine is used as a sanitizer in the present invention it istypically present at a level of from about 0.001% to about 0.4%,preferably from about 0.002% to about 0.3%, and more preferably fromabout 0.05% to about 0.2%, by weight of the usage composition. In somecases, a level of from about 1% to about 2% may be needed for virucidalactivity.

[0155] Other useful biguanide compounds include Cosmoci® CQ®, Vantocil®IB, including poly (hexamethylene biguanide) hydrochloride. Other usefulcationic antimicrobial agents include the bis-biguanide alkanes. Usablewater soluble salts of the above are chlorides, bromides, sulfates,alkyl sulfonates such as methyl sulfonate and ethyl sulfonate,phenylsulfonates such as p-methylphenyl sulfonates, nitrates, acetates,gluconates, and the like.

[0156] Examples of suitable bis biguanide compounds are chlorhexidine;1,6-bis-(2-ethylhexylbiguanidohexane)dihydrochloride;1,6-di-(N₁,N₁′-phenyldiguanido-N₅,N₅′)-hexane tetrahydrochloride;1,6-di-(N₁,N₁′-phenyl-N₁,N₁′-methyldiguanido-N₅,N₅′)-hexanedihydrochloride; 1,6-di(N₁,N₁′-o-chlorophenyldiguanido-N₅,N₅′)-hexanedihydrochloride; 1,6-di(N₁,N₁′-2,6-dichlorophenyldiguanido-N₅,N₅′)hexanedihydrochloride; 1,6-di[N₁,N₁′-.beta.-(p-methoxyphenyl)diguanido-N₅,N₅′]-hexane dihydrochloride;1,6-di(N₁,N₁′-.alpha.-methyl-.beta.-phenyldiguanido-N₅,N₅′)-hexanedihydrochloride; 1,6-di(N₁,N₁′-p-nitrophenyldiguanido-N₅,N₅′)hexanedihydrochloride;.omega.:.omega.′-di-(N₁,N₁′-phenyldiguanido-N₅,N₅′)-di-n-propyletherdihydrochloride;.omega:omega′-di(N₁,N₁′-p-chlorophenyldiguanido-N₅,N₅′)-di-n-propylethertetrahydrochloride;1,6-di(N₁,N₁′-2,4-dichlorophenyldiguanido-N₅,N₅′)hexanetetrahydrochloride; 1,6-di(N₁,N₁′-p-methylphenyldiguanido-N₅,N₅′)hexanedihydrochloride;1,6-di(N₁,N₁′-2,4,5-trichlorophenyldiguanido-N₅,N₅′)hexanetetrahydrochloride; 1,6-di[N₁,N₁′-.alpha.-(p-chlorophenyl)ethyldiguanido-N₅,N₅′] hexanedihydrochloride;.omega.:.omega.′di(N₁,N₁′-p-chlorophenyldiguanido-N₅,N₅′)m-xylenedihydrochloride; 1,12-di(N₁,N₁′-p-chlorophenyldiguanido-N₅,N₅′) dodecanedihydrochloride; 1,10-di(N₁,N₁′-phenyldiguanido-N₅,N₅′)-decanetetrahydrochloride; 1,12-di(N₁,N₁′-phenyldiguanido-N₅,N₅′) dodecanetetrahydrochloride; 1,6-di(N₁,N₁′-o-chlorophenyldiguanido-N₅,N₅′) hexanedihydrochloride; 1,6-di(N₁,N₁′-p-chlorophenyldiguanido-N₅,N₅′)-hexanetetrahydrochloride; ethylene bis (1-tolyl biguanide); ethylene bis(p-tolyl biguanide); ethylene bis(3,5-dimetbylphenyl biguanide);ethylene bis(p-tert-amylpbenyl biguanide); ethylene bis(nonylphenylbiguanide); ethylene bis (phenyl biguanide); ethylene bis (N-butylphenylbiguanide); ethylene bis (2,5-diethoxyphenyl biguanide); ethylenebis(2,4-dimethylphenyl biguanide); ethylene bis(o-diphenylbiguanide);ethylene bis(mixed amyl naphthyl biguanide); N-butyl ethylenebis(phenylbiguanide); trimethylene bis(o-tolyl biguanide); N-butyltrimethylene bis(phenyl biguanide); and the correspondingpharmaceutically acceptable salts of all of the above such as theacetates; gluconates; hydrochlorides; hydrobromides; citrates;bisulfites; fluorides; polymaleates; N-coconutalkylsarcosinates;phosphites; hypophosphites; perfluorooctanoates; silicates; sorbates;salicylates; maleates; tartrates; fumarates;ethylenediaminetetraacetates; iminodiacetates; cinnamates; thiocyanates;arginates; pyromellitates; tetracarboxybutyrates; benzoates; glutarates;monofluorophosphates; and perfluoropropionates, and mixtures thereof.Preferred antimicrobials from this group are1,6-di-(N₁,N₁′-phenyldiguanido-N₅,N₅′)-hexane tetrahydrochloride;1,6-di(N₁,N₁′-o-chlorophenyldiguanido-N₅,N₅′)-hexane dihydrochloride;1,6-di(N₁,N₁′-2,6-dichlorophenyldiguanido-N₅,N₅′)hexane dihydrochloride;1,6-di(N₁,N₁′-2,4-dichlorophenyldiguanido-N₅,N₅′)bexanetetrahydrochloride;1,6-di[N₁,N₁′-.alpha.-(p-chlorophenyl)ethyldiguanido-N₅,N₅′]hexanedihydrochloride;.omega.:.omega.′di(N₁,N₁′-p-chlorophenyldiguanido-N₅,N₅′)m-xylenedihydrochloride; 1,12-di(N₁,N₁′-p-chlorophenyldiguanido-N₅,N₅′) dodecanedihydrochloride; 1,6-di(N₁,N₁′-o-chlorophenyldiguanido-N₅,N₅′) hexanedihydrochloride; 1,6-di(N₁,N₁′-p-chlorophenyldiguanido-N₅,N₅′)-hexanetetrahydrochloride; and mixtures thereof; more preferably,1,6-di(N₁,N₁′-o-chlorophenyldiguanido-N₅,N₅′)-hexane dihydrochloride;1,6-di(N₁,N₁′-2,6-dichlorophenyldiguanido-N₅,N₅′)hexane dihydrochloride;1,6-di(N₁,N₁′-2,4-dichlorophenyldiguanido-N₅,N₅′)hexanetetrahydrochloride;1,6-di[N₁,N₁′-.alpha.-(p-chlorophenyl)ethyldiguanido-N₅,N₅′]hexanedihydrochloride;.omega.:.omega.′di(N₁,N₁′-p-chlorophenyldiguanido-N₅,N₅′)m-xylene dihydrochloride;1,12-di(N₁,N₁′-p-chlorophenyldiguanido-N₅,N₅′) dodecane dihydrochloride;1,6-di(N₁,N₁′-o-chlorophenyldiguanido-N₅,N₅′) hexane dihydrochloride;1,6-di(N₁,N₁′-p-chlorophenyldiguanido-N₅,N₅′)-hexane tetrahydrochloride;and mixtures thereof. As stated hereinbefore, the bis biguanide ofchoice is chlorhexidine its salts, e.g., digluconate, dihydrochloride,diacetate, and mixtures thereof.

[0157] Quaternary Compounds.

[0158] A wide range of quaternary compounds can also be used asantimicrobial actives, in conjunction with the preferred surfactants,for compositions of the present invention that do not containcyclodextrin. Non-limiting examples of useful quaternary compoundsinclude: (1) benzalkonium chlorides and/or substituted benzalkoniumchlorides such as commercially available Barquat® (available fromLonza), Maquat® (available from Mason), Variquat® (available fromWitco/Sherex), and Hyamine® (available from Lonza); (2) di(C₆-C₁₄)alkyldi short chain (C₁₋₄ alkyl and/or hydroxyalkl) quaternary such asBardac® products of Lonza, (3) N-(3-chloroallyl) hexaminium chloridessuch as Dowicide® and Dowicil® available from Dow; (4) benzethoniumchloride such as Hyamine® 1622 from Rohm & Haas; (5) methylbenzethoniumchloride represented by Hyamine® 10X supplied by Rohm & Haas, (6)cetylpyridinium chloride such as Cepacol chloride available from ofMerrell Labs. Examples of the preferred dialkyl quaternary compounds aredi(C₈-C₁₂)dialkyl dimethyl ammonium chloride, such asdidecyldimethylammonium chloride (Bardac 22), anddioctyldimethylammonium chloride (Bardac 2050). Typical concentrationsfor biocidal effectiveness of these quaternary compounds range fromabout 0.001% to about 0.8%, preferably from about 0.005% to about 0.3%,more preferably from about 0.01% to about 0.2%, and even more preferablyfrom about 0.03% to about 0.1%, by weight of the usage composition. Thecorresponding concentrations for the concentrated compositions are fromabout 0.003% to about about 2%, preferably from about 0.006% to about1.2%, and more preferably from about 0.1% to about 0.8% by weight of theconcentrated compositions.

[0159] Surfactants, when added to the antimicrobials tend to provideimproved antimicrobial action. This is especially true for the siloxanesurfactants, and especially when the siloxane surfactants are combinedwith the chlorhexidine antimicrobial actives.

[0160] 9. Cyclodextrin-incompatible Skin Conditioning Agents

[0161] Compositions of the invention can further comprise a safe andeffective amount of a cyclodextrin-incompatible skin conditioning agent.The cyclodextrin-incompatible skin conditioning agent is useful in skinmoisturizing compositions for lubricating the skin, increasing thesmoothness and suppleness of the skin, preventing or relieving drynessof the skin, hydrating the skin, and/or protecting the skin. The skinconditioning agent enhances the skin appearance benefits provided bycomponents of the composition. The cyclodextrin-incompatible skinconditioning agent is preferably selected from the group consisting ofemollients, humectants, moisturizers and mixtures thereof. Thecyclodextrin-incompatible skin conditioning agent is typically presentat a level of at least about 0.1%, more preferably from about 1% toabout 99%, even more preferably from about 1% to about 50%, still morepreferably from about 2% to about 30% and most preferably from about 5%to about 25% (e.g., about 5% to about 10% or 15%). Thecyclodextrin-incompatible skin conditioning agents of the presentinvention have complexation constants with cyclodextrin of greater thanabout 5,000 M⁻¹, preferably greater than about 8,000 M⁻¹, and morepreferably greater than about 10,000 M⁻¹.

[0162] A variety of emollients can be employed. These emollients may beselected from one or more of the following classes: Triglyceride esters;Acetoglyceride esters; Alkyl esters of fatty acids having 10 to 20carbon atoms; Alkenyl esters of fatty acids having 10 to 20 carbonatoms; Fatty acids having 10 to 20 carbon atoms; Fatty alcohols having10 to 20 carbon atoms; Lanolin and lanolin derivatives; Polyhydricalcohol esters; Wax esters; Beeswax derivatives; Vegetable waxes;Phospholipids; Sterols including, but not limited to, cholesterol andcholesterol fatty acid esters; and Amides.

[0163] Additional types of cyclodextrin-incompatible skin conditioningagents include humectants of the polyhydric alcohol-type. Also usefulherein are guanidine; glycolic acid and glycolate salts (e.g. ammoniumand quaternary alkyl ammonium); lactic acid and lactate salts (e.g.ammonium and quaternary alkyl ammonium); aloe vera in any of its varietyof forms (e.g., aloe vera gel); sugar and starch derivatives (e.g.,alkoxylated glucose); hyaluronic acid and derivatives thereof (e.g.,salt derivatives such as sodium hyaluraonate); lactamidemonoethanolamine; acetamide monoethanolamine; urea; panthenol; sugars;starches; silicone gums; and mixtures thereof. Also useful are thepropoxylated glycerols described in U.S. Pat. No. 4,976,953, which isdescription is incorporated herein by reference. Other usefulconditioning agents include the various C₁-C₃₀ monoesters and polyestersof sugars and related materials such as described herein in reference tothe hydrophobic component.

[0164] Suitable cyclodextrin-incompatible skin conditioning agents aredescribed in more detail in U.S. Pat. No. 6,001,377 issued Dec. 14, 1999to SaNogueira, Jr. et al., which is incorporated herein by reference.

[0165] 10. Other Ingredients

[0166] Other optional ingredients particularly suitable in the presentcompositions are described in the following, which are herebyincorporated herein by reference: U.S. Pat. No. 5,714,137 issued Feb. 3,1998 to Trinh et al.; U.S. Pat. No. 5,942,217 issued Aug. 24, 1999 toWoo et al.; U.S. Pat. No. 6,001,343 issued Dec. 14, 1999 to Trinh etal.; International Application No. PCT/US98108124, filed Apr. 27, 1998,and published Nov. 4, 1999 as WO99/55816 by Woo et al. (P&G Case 7097);International Application No. PCT/US98/08129, filed Apr. 27, 1998, andpublished Nov. 4, 1999 as WO99/55950 by Hubesch et al. (P&G CaseCM-1714).

[0167] II. Process Of Manufacture

[0168] Compositions of the present invention that comprise low-degree ofsubstitution cyclodextrin derivatives can be manufactured by combiningand/or mixing together the components of the composition.

[0169] When the present compositions comprise low-degree of substitutioncyclodextrin derivatives, cyclodextrin-incompatible material, andcyclodextrin-compatible material, the process of manufacturing thepresent compositions can be important to provide the preferredfunctionally-available cyclodextrin in the compositions. To maintainfunctionally-available cyclodextrin in the composition, the presentcompositions can be made by first combining cyclodextrin-incompatiblematerials together with cyclodextrin-compatible surfactant. This resultsin the formation of molecular aggregates, such as miscelles or vesicles,in which the cyclodextrin-incompatible materials are maintained. Onlyafter the cyclodextrin-incompatible materials are combined withcyclodextrin-compatible surfactant, is the cyclodextrin added to formthe present compositions. As a result, the compositions havefunctionally-available cyclodextrin due to the tendency of thecyclodextrin-incompatible materials to remain within the molecularaggregates that they form with cyclodextrin-compatible surfactant,effectively keeping the cyclodextrin-incompatible materials away fromthe cavities of the cyclodextrin molecules. This allows forfunctionally-available cyclodextrin in the present compositions.

[0170] When the present compositions comprise functionally-availablecyclodextrin, cyclodextrin-incompatible material, andcyclodextrin-compatible material, the present process of manufacturing acomposition suitable for capturing unwanted molecules comprises thesteps of:

[0171] (a) providing cyclodextrin, a cyclodextrin-compatible material,and a cyclodextrin-incompatible material;

[0172] (b) combining said cyclodextrin-compatible material and saidcyclodextrin-incompatible material to form a first mixture; and

[0173] (c) subsequently combining said cyclodextrin with said firstmixture to form said composition suitable for capturing unwantedmolecules.

[0174] The components utilized in the present processes of manufacture,as well as the compositions produced by the processes, are describedhereinbefore. The processes can also comprise combining thecyclodextrin-compatible material and the cyclodextrin-incompatiblematerial with water to form a first aqueous mixture and subsequentlyadding cyclodextrin to the first aqueous mixture to form the compositionsuitable for capturing unwanted molecules. The present processes canalso comprise combining the cyclodextrin-compatible material and thecyclodextrin-incompatible material to form a first mixture, combiningthe cyclodextrin with water to form a second aqueous mixture andcombining the first mixture and the second aqueous mixture to form thecomposition suitable for capturing unwanted molecules.

[0175] III. Methods of Use

[0176] The stable compositions of the present invention comprisinglow-degree of substitution cyclodextrin are suitable for removingunwanted molecules, such as malodorous molecules, from surfaces,especially inanimate surfaces including fabrics, including carpets, andhousehold surfaces such as countertops, dishes, floors, garbage cans,ceilings, walls, carpet padding, air filters, and the like, and animatesurfaces, including skin, hair, and the like. The method of the presentinvention comprises contacting a surface containing unwanted moleculeswith a stable composition comprising functionally-available cyclodextrinand a cyclodextrin-incompatible material. As used herein, the term“unwanted molecules” refers to molecules that are desirably reduced orremoved from surfaces for aesthetic or safety reasons, such asmalodorous molecules. Unwanted molecules have a relatively strongtendency to complex with cyclodextrin, such that when the presentcompositions comprising functionally-available cyclodextrin come incontact with the unwanted molecules, the unwanted molecules will complexwith the functionally-available cyclodextrin which effectively removesor reduces the presence of the unwanted molecules on the treatedsurface.

[0177] Unwanted molecules complex with the functionally-availablecyclodextrin either by simply complexing with uncomplexed cyclodextrinin the present compositions, or by replacing molecules that are weaklycomplexed with the functionally-available cyclodextrin due to thestronger affinity of the cyclodextrin to complex with the unwantedmolecules. In this instance, a replacement occurs wherein the weaklycomplexed molecule is replaced by the unwanted molecule in the cavity ofthe functionally-available cyclodextrin. As such, the unwantedmolecules, or mixtures thereof, generally, and preferably, have acomplexation constant that is greater than the complexation constant ofmolecules that are weakly complexed with cyclodextrin in the presentcompositions.

[0178] The present compositions can contain components which make themsuitable for a variety of applications, including but not limited to,laundry detergent compositions, fabric softening compositions, hardsurface cleaning compositions, dishwashing detergent compositions,malodor controlling compositions, shampoo compositions, hair conditionercompositions, personal cleansing compositions, underarm deodorantcompositions, and the like.

[0179] For controlling odor on fabrics, especially dry fabrics, thepresent compositions are preferably used as a spray. It is preferablethat the usage compositions of the present invention contain low levelsof cyclodextrin so that a visible stain does not appear on the fabric atnormal usage levels. Preferably, the solution used to treat the surfaceunder usage conditions is virtually not discernible when dry. Typicallevels of total cyclodextrin in usage compositions for usage conditionsare from about 0.01% to about 5%, preferably from about 0.1% to about4%, more preferably from about 0.5% to about 2% by weight of thecomposition. Usage compositions will typically have at least about0.001%, preferably at least about 0.01%, and more prefearbly at leastabout 0.1%, by weight of the composition of functionally-availablecyclodextrin. Compositions with higher concentrations can leaveunacceptable visible stains on fabrics as the solution evaporates off ofthe fabric. This is especially a problem on thin, colored, syntheticfabrics. In order to avoid or minimize the occurrence of fabricstaining, it is preferable that the fabric be treated at a level of lessthan about 5 mg of cyclodextrin per gram of fabric, more preferably lessthan about 2 mg of cyclodextrin per gram of fabric. The presence of asurfactant can improve appearance by minimizing localized spotting.

[0180] IV. Test Methods

[0181] A. Measurement of Complexation Constants

[0182] A spectral displacement method with phenolphthalein is used todetermine the complexation constant between cyclodextrin and a givenmaterial, especially for surfactants. This method of determiningcomplexation constants with cyclodextrins is described in detail in thefollowing references, which are hereby incorporated herein by reference:Sasaki, K. J., Christian, S. D., and Tucker, E. E., “Study of theStability of 1:1 Complexes Between Aliphatic Alcohols andb-Cyclodextrins in Aqueous Solution,” Fluid Phase Equilibria, Vol. 49,(Amsterdam, Elsevier Science Publishers, 1989), pp. 281-89; and Wilson,L. D., Siddall, S. R., and Verrall R. E., “A Spectral Displacement Studyof the Binding Constants of Cyclodextrin-Hydrocarbon and—FluorocarbonSurfactant Inclusion Complexes,” Canadian Journal of Chemistry, Vol. 75,(NRC Canada 1997), pp. 927-933.

[0183] The complexation constant of a given material with cyclodextrinis obtained by an absorbance measurement in the visible region at 550 nmthat is performed with a spectrophotometer at room temperature. Allsolutions are prepared in 4.0×10⁻³ mol/l Na₂CO₃ solution to maintain aconstant pH. The concentration of phenolphthalein is kept constant at3.0×10⁻⁵ mol/l. Cyclodextrin concentration and surfactant concentrationare varied. Here, optimum parameter values for absorption coefficient ofphenolphthalein at 550 nm is 33,000 M⁻¹cm⁻¹, and the complexationconstants of phenolphthalein with cyclodextrin and cyclodextrinderivatives are preliminary obtained. For example, the complexationconstant of phenolphthalein with beta-cyclodextrin is about 21,000 M⁻¹.Complexation constants of cyclodextrin-compatible and/orcyclodextrin-incompatible materials are determined with using the free,uncomplexed phenolphthalein concentration obtained by absorbance at 550nm.

[0184] B. Malodor Performance Test

[0185] This test method is used to evaluate the effectiveness of acomposition in reducing or removing malodor from fabrics. The testfabrics are first washed in a laundry washer using unscented laundrydetergent and then dried in a laundry dryer. About 80 microliters of asynthetic body malodor composition is uniformly applied over a twosquare inch area of each test fabric. The malodor-treated test fabricsare then sealed in a plastic bag and allowed to equilibrate overnight atambient temperature. Qualified odor graders evaluate the initial malodorlevel of the malodor-treated test fabrics and assign a malodor gradeaccording to the Malodor Evaluation Scale below. The malodor-treatedtest fabrics are then treated with equivalent amounts of the testcompositions by spraying the test compositions onto the test fabrics andallowing the test fabrics to dry. Once the test fabrics have dried, thequalified odor graders again evaluate the malodor level of the testfabrics and assign a malodor grade according to the Malodor EvaluationScale below. Initial malodor grades and after-treatment malodor gradesare recorded and the differences between the grades are calculated toestablish the “Malodor Reduction” value. Malodor Evaluation Scale  0 NoMalodor/Perfume Present  10 I Think There is Malodor/Perfume Present  25Slight Malodor/Perfume Present  50 Moderate Malodor/Perfume Present  75Strong Malodor/Peffume Present 100 Extremely Strong Malodor/PerfumePresent

EXAMPLE I

[0186] The following compositions are evaluated according to the MalodorPerformance Test described hereinbefore in Section IV.B: INGREDIENTS(WT. %) COMPOSITION A B C D 5.5 DOS HPBCD¹ 1.0 — — 0.4 3.3 DOS HPBCD² —0.5 1.0 — BCD³ — — — 0.1 SILWET L-7600 0.1 0.1 0.1 0.1 SodiumPolyacrylate (2500 MW) 0.1 0.1 0.1 0.1 Diethylene Glycol 0.25 0.25 0.250.25 Ethanol 3.0 3.0 3.0 3.0 KATHON (Preservative) 3 ppm 3 ppm 3 ppm 3ppm Perfume 0.1 0.1 0.1 0.1 Distilled Water Balance Balance BalanceBalance COMPOSITION E F G H 5.5 DOS HPBCD¹ 0.75 — — — 3.3 DOS HPBCD² —0.75 — — 12.25 DOS MeBCD⁴ — — 0.75 — 4.2 DOS MeBCD⁵ — — — 0.75 POE-60(Hydrogenated Caster Oil) 0.2 0.2 0.2 0.2 SILWET L-77 0.2 0.2 0.2 0.2Sodium Polyacrylate (2500 MW) 0.1 0.1 0.1 0.1 KATHON (Preservative) 3ppm 3 ppm 3 ppm 3 ppm Perfume 0.06 0.06 0.06 0.06 Distilled WaterBalance Balance Balance Balance

[0187] Compositions A-D are tested according to the Malodor PerformanceTest and the results are reported in the following table: INITIALMALODOR MALODOR MALODOR GRADE AFTER REDUCTION COMPOSITION GRADETREATMENT VALUE A 80 50 30 B 85 35 50 C 85 35 50 D 85 30 55

[0188] These results show that compositions comprising low-degree ofsubstitution cyclodextrin derivatives (e.g. Compositions B and C) orcyclodextrin mixtures (e.g. Composition D) exhibit significantlyimproved performance in regard to capturing unwanted molecules, such asmalodorous molecules, as compared to compositions comprisingcyclodextrin derivatives having a higher average degree of substitution(e.g. Composition A).

[0189] Compositions E-H are tested according to the Malodor PerformanceTest and the results are reported in the following table: COMPOSITIONAVERAGE MALODOR REDUCTION VALUE E 37.1 F 45.7 G 42.5 H 55

[0190] These results show that compositions comprising low-degree ofsubstitution cyclodextrin derivatives exhibit significantly improvedperformance in regard to capturing unwanted molecules, such asmalodorous molecules, as compared to compositions comprisingcyclodextrin derivatives having a higher average degree of substitution(comparing Composition E vs. F and Composition G vs. H).

EXAMPLE II

[0191] The following are additional non-limiting Examples of thecompositions of the present invention. Examples I J K L M Ingredients Wt% Wt % Wt % Wt % Wt % 5.5 DOS HPBCD¹ 0.5 — 0.25 — 0.35 4.2 DOS MeBCD⁵ —0.25 — 0.5 — Cartaretin F-23⁶ 1.0 — — — — Copolymer 937⁷ — 0.3 — — —Copolymer 958⁸ — — 0.4 — — Diaformer Z-SM⁹ — — — 0.5 — Vinex 2019¹⁰ — —— — 0.5 D5 volatile silicone 0.25 — 0.5 0.2 — PDMS 10,000 cst — 0.25 —0.2 — Silwet L-7600 0.3 — — — 0.1 Silwet L-7602 — 0.25 — 0.4 — SilwetL-7622 — — 0.5 — — Diethylene glycol — — 0.2 — — Propylene glycol 0.06 —— — 0.1 Perfume 0.1 0.05 0.05 0.1 0.05 Kathon 3 ppm 3 ppm 3 ppm 3 ppm 3ppm Distilled water Bal. Bal. Bal. Bal. Bal.

What is claimed is:
 1. A composition for capturing unwanted molecules,said composition comprising low-degree of substitution cyclodextrinderivative.
 2. A composition according to claim 1 wherein saidlow-degree of substitution cyclodextrin derivative is selected from thegroup consisting of low-degree of substitution hydroxyalkylcyclodextrin, low-degree of substitution alkylated cyclodextrin, andmixtures thereof.
 3. A composition according to claim 2 wherein saidlow-degree of substitution cyclodextrin derivative is selected from thegroup consisting of hydroxyalkyl cyclodextrin having an average degreeof substitution of less than about 5.0, alkylated cyclodextrin having anaverage degree of substitution of less than about 6.0, and mixturesthereof.
 4. A composition according to claim 3 wherein said low-degreeof substitution cyclodextrin derivative is selected from the groupconsisting of hydroxyalkyl cyclodextrin having an average degree ofsubstitution of less than about 4.5, alkylated cyclodextrin having anaverage degree of substitution of less than about 5.5, and mixturesthereof.
 5. A composition according to claim 1 wherein said low-degreeof substitution cyclodextrin derivative is selected from the groupconsisting of alpha-cyclodextrin derivatives, beta-cyclodextrinderivatives, gamma-cyclodextrin derivatives, and mixtures thereof.
 6. Acomposition according to claim 5 wherein said low-degree of substitutioncyclodextrin derivative is a beta-cyclodextrin derivative selected fromthe group consisting of low-degree of substitutionhydroxyalkyl-beta-cyclodextrin, low-degree of substitutionalkylated-beta-cyclodextrin, and mixtures thereof.
 7. A compositionaccording to claim 6 wherein said beta-cyclodextrin derivative is ahydroxyalkyl beta-cyclodextrin having an average degree of substitutionof less than about 4.0.
 8. A composition according to claim 7 whereinsaid hydroxyalkyl beta-cyclodextrin is hydroxypropyl beta-cyclodextrinhaving an average degree of substitution of about 3.3.
 9. A compositionaccording to claim 7 wherein said alkylated beta-cyclodextrin ismethylated beta-cyclodextrin having an average degree of substitution ofabout 4.2.
 10. A composition according to claim 1 wherein saidcomposition further comprises non-derivatized cyclodextrin selected fromthe group consisting of alpha-cyclodextrin, beta-cyclodextrin,gamma-cyclodextrin, and mixtures thereof.
 11. A composition forcapturing unwanted molecules, said composition comprising a cyclodextrinmixture comprising a cyclodextrin derivative having an average degree ofsubstitution greater than that of low-degree of substitutioncyclodextrin derivative, and either a low-degree of substitutioncyclodextrin derivative or a non-derivatized cyclodextrin, wherein thecyclodextrin mixture effectively has an average degree of substitutionequal to that of a low-degree of substitution cyclodextrin derivative.12. A process of manufacturing a composition suitable for capturingunwanted molecules comprising the steps of: (a) providing low-degree ofsubstitution cyclodextrin, a cyclodextrin-compatible surfactant, and acyclodextrin-incompatible surfactant; (b) combining saidcyclodextrin-compatible surfactant and said cyclodextrin-incompatiblesurfactant to form a first mixture; and (c) subsequently combining saidlow-degree of substitution cyclodextrin with said first mixture to formsaid composition suitable for capturing unwanted molecules.
 13. Aprocess according to claim 12 wherein said process comprises combiningsaid cyclodextrin-compatible surfactant and saidcyclodextrin-incompatible surfactant with water to form a first aqueousmixture and subsequently adding low-degree of substitution cyclodextrinto said first aqueous mixture to form said composition suitable forcapturing unwanted molecules.
 14. A process according to claim 12wherein said process comprises combining said cyclodextrin-compatiblesurfactant and said cyclodextrin-incompatible surfactant to form a firstmixture, combining said low-degree of substitution cyclodextrin withwater to form a second aqueous mixture and combining the first mixtureand the second aqueous mixture to form said composition suitable forcapturing unwanted molecules.
 15. A process according to claim 12wherein said first mixture comprises said cyclodextrin-incompatiblesurfactant solubilised in micelles or vesicles comprising saidcyclodextrin-compatible surfactant as molecular aggregates.
 16. A methodof capturing unwanted molecules from a surface comprising applying tothe surface a composition according to claim 1 and allowing thecomposition to dry.